Name: 34301-54-7|Adamantane-1-thiol|95%
Brand: Ambeed
SKU: A721944
Price: 5.0 USD
Availability: InStock
Rating: 94 (28 reviews)

1
[ 1131-48-2 ]
[ 34301-54-7 ]
[ 76053-45-7 ]

Reference： [1]Journal of Heterocyclic Chemistry,1991,vol. 28,p. 1051 - 1060

2
[ 1131-61-9 ]
[ 34301-54-7 ]
[ 136887-29-1 ]
[ 136887-30-4 ]

Reference： [1]Journal of Heterocyclic Chemistry,1991,vol. 28,p. 1051 - 1060

3
[ 1131-61-9 ]
[ 34301-54-7 ]
[ 108-24-7 ]
[ 136887-29-1 ]
[ 136887-30-4 ]
[ 136887-37-1 ]

Reference： [1]Journal of Heterocyclic Chemistry,1991,vol. 28,p. 1051 - 1060

4
[ 34301-54-7 ]
[ 281-23-2 ]

Yield	Reaction Conditions	Operation in experiment
73%	With aluminum oxide; sodium triethylborohydride; iron(II) chloride In tetrahydrofuran; benzene Ambient temperature;
70%	With tungsten hexacarbonyl In chlorobenzene Heating;
	Stage #1: 1-Adamantanethiol With hexan-1-amine; tributylphosphine; eosin y for 0.0833333h; Inert atmosphere; Sealed tube; Stage #2: at 23℃; for 1h; Inert atmosphere; Sealed tube; Irradiation;

94 %Spectr.

With di-tert-butyl peroxide; triethyl phosphite In acetonitrile at 25℃; for 6h; Irradiation;

Reference： [1]Alper, Howard; Ripley, Sharon; Prince, Trish L. [Journal of Organic Chemistry, 1983, vol. 48, # 2, p. 250 - 252]
[2]Ng, Chi Tat; Wang, Xiaojun; Luh, Tien-Yau [Journal of Organic Chemistry, 1988, vol. 53, # 11, p. 2536 - 2539]
[3]Discekici, Emre H.; Shankel, Shelby L.; Anastasaki, Athina; Oschmann, Bernd; Lee, In-Hwan; Niu, Jia; McGrath, Alaina J.; Clark, Paul G.; Laitar, David S.; De Alaniz, Javier Read; Hawker, Craig J.; Lunn, David J. [Chemical Communications, 2017, vol. 53, # 11, p. 1888 - 1891]
[4]Qiu, Wenting; Shi, Shuai; Li, Ruining; Lin, Xianfeng; Rao, Liangming; Sun, Zhankui [Chinese Journal of Chemistry, 2021, vol. 39, # 5, p. 1255 - 1258]

5
[ 34301-54-7 ]
[ 34895-45-9 ]

Yield	Reaction Conditions	Operation in experiment
90%	With sodium methoxide In methanol at 20℃; for 10h; Green chemistry;	A typical procedure for the preparation of symmetrical disulfides General procedure: A variety of thiols (10mmol) were added into sodium methoxide 30 wt. % in methanol(1.85 mL, 10mmol) (NaOMe/MeOH-30), and the solution was stirred at room temperatureunder air atmosphere. After completion of the reaction, the desired products wereextracted with ethyl acetate or n-hexane (3×2mL). The collected extracts were driedover Na2SO4 and concentrated under reduced pressure. The pure symmetrical disulfideswere obtained as liquids or solids. The known and new products were characterized andidentified by melting point, FT-IR, 1HNMR and 13C NMR, and mass analysis.
84%	With sodium hydroxide; potassium hexacyanoferrate(III) In lithium hydroxide monohydrate Ambient temperature;
83%	With potassium permanganate In neat (no solvent) at 60℃; for 0.166667h; Microwave irradiation;	4.2.3. Solvent-free oxidative coupling of captopril into captopril disulfide by groundpotassium permanganate under microwave irradiation (Method C) General procedure: A test tube (h = 8.5 cm, d = 1.2 cm) containing a pertinent quantity of finely groundpotassium permanganate (1mmol, 0.158 g) and captopril (3mmol, 0.652 g) was placed in amicrowave oven, where the mixture of reactants was exposed to microwave irradiation for10 min at 60°C. After cooling, the reaction mixturewas extractedwith 30mLmethanol andthen filtered through a 1.5-2 cm layer of celite 545. The filtrate was poured into a 100mLbeaker containing warm water, then the solution was vaporized gradually by heating untilthe crystal appearance. The product crystals were filtered, washed with water, dried in thedesiccator overnight and characterized by HRMS, 1H and 13C NMR spectroscopy.

60%	With potassium permanganate In neat (no solvent) at 20℃; for 5h; Sonication;	4.2.2. Solvent-free oxidative coupling of 2-methyl-2-propanethiol into di-tert-butyldisulfide by ground potassium permanganate under ultrasound irradiation (MethodB) General procedure: A test tube (h = 16.0 cm, d = 1.4 cm) containing a pertinent quantity of finely groundpotassium permanganate (1mmol, 0.158 g) and 2-methyl-2-propanethiol (3mmol, 0.27 g)was placed in an ultrasonic bath, where the mixture of reactants was exposed to ultrasoundirradiation for 135 min. Subsequently, the reaction mixture was worked up as described inmethod A.
	Multi-step reaction with 2 steps 1: SO₂Cl₂, pyridine / diethyl ether / 0.5 h / -78 °C 2: pyridine / diethyl ether / 0.5 h

Reference： [1]Ling, Ong Chiu; Heidelberg, Thorsten; Ching, Juan Joon; Khaligh, Nader Ghaffari [Journal of Sulfur Chemistry, 2021, vol. 42, # 3, p. 281 - 294]
[2]Jorgensen, Flemming S.; Snyder, James P. [Journal of Organic Chemistry, 1980, vol. 45, # 6, p. 1015 - 1020]
[3]Dao, Xuan-Tien; Luu, Thi Xuan Thi; Nguyen, Ngan-Giang Thi; Nguyen, Ngoc-Huy; Nguyen, Xuan-Triet [Journal of Sulfur Chemistry, 2022]
[4]Dao, Xuan-Tien; Luu, Thi Xuan Thi; Nguyen, Ngan-Giang Thi; Nguyen, Ngoc-Huy; Nguyen, Xuan-Triet [Journal of Sulfur Chemistry, 2022]
[5]Derbesy, Gerard; Harpp, David N. [Tetrahedron Letters, 1994, vol. 35, # 30, p. 5381 - 5384]

6
[ 34301-54-7 ]
1-adamantylthionitrite [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With tert.-butylnitrite In dichloromethane; <i>tert</i>-butyl alcohol at 20℃; for 0.5h; Inert atmosphere;
73%	With sulfuric acid; sodium nitrite In water; benzene at 0℃; for 0.666667h;

Reference： [1]Bakhoda, Abolghasem; Bertke, Jeffery A.; Hosseininasab, Valiallah; McQuilken, Alison C.; Timerghazin, Qadir K.; Warren, Timothy H. [Angewandte Chemie - International Edition, 2020, vol. 59, # 27, p. 10854 - 10858][Angew. Chem., 2020, vol. 132, # 27, p. 10946 - 10950,5]
[2]Girard, Pierre; Guillot, Nadine; Motherwell, William B.; Hay-Motherwell, Robyn S.; Potier, Pierre [Tetrahedron, 1999, vol. 55, # 12, p. 3573 - 3584]

7
[ 34301-54-7 ]
1,2'-diadamantyl disulfide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	With oxygen In methanol at 40℃; for 2h;

Reference： [1]Arisawa, Mieko; Sugata, Chiyoshi; Yamaguchi, Masahiko [Tetrahedron Letters, 2005, vol. 46, # 36, p. 6097 - 6099]

8
[ 34301-54-7 ]
methyl 5-acetamido-2,4,7,8,9-penta-O-acetyl-3,5-dideoxy-D-glycero-D-galacto-2-nonulopyranosonate [ No CAS ]
[ 956107-37-2 ]

Yield	Reaction Conditions	Operation in experiment
81%	With boron trifluoride diethyl etherate In dichloromethane at 20℃;

Reference： [1]Crich, David; Li, Wenju [Journal of Organic Chemistry, 2007, vol. 72, # 20, p. 7794 - 7797]

9
[ 34301-54-7 ]
[ 27639-75-4 ]

Yield	Reaction Conditions	Operation in experiment
77%	Stage #1: 1-Adamantanethiol With triethylamine In propan-1-ol at 20℃; for 0.333333h; Stage #2: With 3,4-dichloro-1,2,5-thiadiazole In propan-1-ol for 0.833333h;	2.1. General procedure General procedure: The thiol (5 mmol) and 5.5 mmol of triethylamine (5.5 mmol) were dissolved in 5mL of 1-propanol and stirred for 20min. Then, 3,4-dichloro-1,2,5-thiadiazole (2.5mmol) in 5mL 1-propanol was added dropwise into the flask. The mixture was stirred for the appropriatetime (Table 2) until 3,4-dichloro-1,2,5-thiadiazole was fully consumed (monitored byTLC), and then an aqueous solution of HCl (5 mL) was added, and the mixture stirredfor 20 min. During this time, ethanedinitrile and triethylammonium chloride were dissolvedinto water and the desired trisulfide was easily extracted by the ethyl acetate (3 ×5 mL). The trisulfides were isolated in the 74-85% yields. The pure liquid trisulfides wereobtained after solvent removal. The more pure solid trisulfides could be formed by recrystallizationproducts from the n-hexane and ethyl acetate mixture. The melting points forsolid products are reported in Table 2.Note: due to the toxicity of cyanogen gas, it needs to be trapped as oxamide or stored asgas for future applications.Compounds 2b [30], 2d [52], 2e [51], 2f [53], 2 g [54], 2h [52], 2i [24], and 2k [21]were characterized previously.
	Multi-step reaction with 2 steps 1: aq. H₂O₂ 2: aq. Me₂NH / methanol

Reference： [1]Gorjian, Hayedeh; Khaligh, Nader Ghaffari [Journal of Sulfur Chemistry, 2022, vol. 43, # 2, p. 169 - 179]
[2]Sirakawa,K. et al. [Chemical and pharmaceutical bulletin, 1970, vol. 18, # 2, p. 235 - 242]

10
[ 34301-54-7 ]
[ 14267-92-6 ]
[ 1010447-22-9 ]

Yield	Reaction Conditions	Operation in experiment
95%	Stage #1: 1-Adamantanethiol With potassium hydroxide In methanol for 0.25h; Inert atmosphere; Stage #2: 1-chloro-4-pentyne In methanol at 50℃; for 2h;

Reference： [1]Bencivenni, Giorgio; Lanza, Tommaso; Leardini, Rino; Minozzi, Matteo; Nanni, Daniele; Spagnolo, Piero; Zanardi, Giuseppe [Organic Letters, 2008, vol. 10, # 6, p. 1127 - 1130]

11
[ 34301-54-7 ]
[ 67602-05-5 ]
[ 1262118-49-9 ]

Yield	Reaction Conditions	Operation in experiment
62%	Stage #1: 1-Adamantanethiol With sodium hydride In acetonitrile for 0.25h; Stage #2: 2-amino-3-bromo-5-phenylpyrazine In acetonitrile at 80℃; for 4h;	2-Amino-5-phenyl-3-adamantylthiopyrazine (18o).; To a solution of 1 -adamantanethiol (0.07 g, 0.4 mmol) in dry acetonitrile (10 mL), sodium hydride (NaH) (9 mg, 0.4 mmol) was added and the resulting mixture was stirred for 15 min. After this time 2-amino-3-bromo-5-phenylpyrazine 17b (0.05 g, 0.2 mmol) was added and the mixture heated at 800C for 4h, cooled and quenched with water. Then EtOAc was added and the organic layer was anidrified over Na2SO4, filtered and the solvent removed under reduced pressure to get a crude that was purified by flash chromatography using petroleum ether-EtOAc (7:3 v/v) as eluent, to obtain 0.04 g of the title compound 18o as a yellow oil (62% yield). 1H-NMR (CDCl3): 1.73 (s, 6H), 2.08 (s, 3H), 2.23 (s, 6H), 5.13 (br s, 2H), 7.32- 7.36 (m, IH), 7.42-7.46 (m, 2H), 7.91-7.93 (m, 2H), 8.29 (s, IH). MS (ESI): m/z 338 (M+H+).

Reference： [1]Current Patent Assignee: UNIVERSITA DEGLI STUDI DI SIENA - WO2011/7314, 2011, A1 Location in patent: Page/Page column 35

12
[ 34301-54-7 ]
[ 1343493-41-3 ]
[ 1343493-44-6 ]

Yield	Reaction Conditions	Operation in experiment
68%	With 2,2'-azobis(isobutyronitrile) In 1,4-dioxane at 70℃; Inert atmosphere;	To a solution of disaccharide 6 (1 mmol) in anhydrous dioxane (10 mL) maintained under an inert atmosphere was added the desired thiol (5 mol equiv) followed by addition of catalytic 2,2'-azobis(2-methylpropionitrile). The reaction mixture was stirred at 70 °C for 3-4 h. After the completion of the reaction, a few drops of cyclohexene were added and were concentrated under reduced pressure. The crude product was subjected to chromatographic purification to get the pure disaccharide (7a-c).

Reference： [1]Location in patent: experimental part Mugunthan; Sriram, Dharmarajan; Yogeeswari, Perumal; Kartha, K.P. Ravindranathan [Carbohydrate Research, 2011, vol. 346, # 15, p. 2401 - 2405]

13
[ 34301-54-7 ]
[ 2905-69-3 ]
[ 1353055-81-8 ]
[ 1353055-82-9 ]
[ 50-79-3 ]

Yield	Reaction Conditions	Operation in experiment
68%Chromat.; 6%Chromat.		General procedure: The following procedure is representative of these reactions. PhSH (5 mmol) and t-BuOK (5.1 mmol) were added to 250 mL of distilled liquid ammonia; PhS- ions were ready for use. The substrate, <strong>[2905-69-3]methyl 2,5-dichlorobenzoate</strong> (1 mmol), was added to the solution, and the reaction mixture was irradiated for 2 h. The reaction was then quenched with an excess of ammonium nitrate (or methyl iodide), and the ammonia was allowed to evaporate. The solid was dissolved in water, and HNO3 was added to the water phase to reach pH=3 before extraction with diethyl ether. Products were isolated by column chromatography employing silica gel and quantified by GC using the internal standard method.

Reference： [1]Tetrahedron,2012,vol. 68,p. 584 - 589

14
[ 34301-54-7 ]
[ 6597-78-0 ]
[ 1353055-84-1 ]
[ 1918-00-9 ]

Yield	Reaction Conditions	Operation in experiment
98%Chromat.		General procedure: The following procedure is representative of these reactions. PhSH (5 mmol) and t-BuOK (5.1 mmol) were added to 250 mL of distilled liquid ammonia; PhS- ions were ready for use. The substrate, methyl 2,5-dichlorobenzoate (1 mmol), was added to the solution, and the reaction mixture was irradiated for 2 h. The reaction was then quenched with an excess of ammonium nitrate (or methyl iodide), and the ammonia was allowed to evaporate. The solid was dissolved in water, and HNO3 was added to the water phase to reach pH=3 before extraction with diethyl ether. Products were isolated by column chromatography employing silica gel and quantified by GC using the internal standard method.

Reference： [1]Tetrahedron,2012,vol. 68,p. 584 - 589

15
[ 34301-54-7 ]
[ 6597-78-0 ]
[ 108-98-5 ]
[ 75355-11-2 ]
[ 1353055-83-0 ]
[ 1353055-84-1 ]
[ 1918-00-9 ]

Yield	Reaction Conditions	Operation in experiment
38%Chromat.; 48%Chromat.; 9%Chromat.		General procedure: The following procedure is representative of these reactions. PhSH (5 mmol) and t-BuOK (5.1 mmol) were added to 250 mL of distilled liquid ammonia; PhS- ions were ready for use. The substrate, methyl 2,5-dichlorobenzoate (1 mmol), was added to the solution, and the reaction mixture was irradiated for 2 h. The reaction was then quenched with an excess of ammonium nitrate (or methyl iodide), and the ammonia was allowed to evaporate. The solid was dissolved in water, and HNO3 was added to the water phase to reach pH=3 before extraction with diethyl ether. Products were isolated by column chromatography employing silica gel and quantified by GC using the internal standard method.

Reference： [1]Tetrahedron,2012,vol. 68,p. 584 - 589

16
[ 34301-54-7 ]
[ 1350519-31-1 ]
[ 1350519-32-2 ]

Yield	Reaction Conditions	Operation in experiment
69%	Stage #1: C₅₁H₆₂N₂O₂₃S With 1,1'-sulfinylbisbenzene; 2,4,6-tri-tert-butylpyrimidine In dichloromethane at 20℃; for 1h; Molecular sieve; Inert atmosphere; Stage #2: With trifluoromethylsulfonic anhydride In dichloromethane at -78℃; for 0.166667h; Stage #3: 1-Adamantanethiol In dichloromethane at -78℃; for 1h;	2; 3A A suspension of the starting phenyl thioglycoside (0.616 mmol), Ph2SO (373 mg, 1 .85 mmol), 2,4,6-Tri-tert-Butyl Pyrimidine (306 mg, 1 .23 mmol) and activated 4A powdered molecular sieves (900 mg) in anhydrous CH2CI2 (8 mL) was stirred at room temperature under argon protection for 1 hr and then cooled down to - 78 °C with dry ice/acetone bath. To the cold reaction mixture was added Tf2O (124 μΙ_, 0.739 mmol) drop wise. After addition, the mixture was stirred for 10 min and then a 1 -adamantanethiol (31 1 mg, 1 .85 mmol) solution in anhydrous CH2CI2 (1 .5 mL) was injected into the mixture drop wise along the inside wall of the cold flask. After addition, the mixture was stirred at - 78 °C for 1 hr and slowly warmed up to room temperature. The reaction mixture was diluted with CH2CI2, filtered through celite, washed with aqueous saturated NaHCO3 solution and brine, dried over Na2SO4, and concentrated under reduced pressure. Purification through silica gel column chromatography (eluent: Heptane/EtOAc) afforded the desired product; The dimer 17 (679 mg, 0.616 mmol) was treated with SOP 7 to give product 18 (449 mg, 0.387 mmol, 69% yield).

Reference： [1]Current Patent Assignee: INTERNATIONAL CHEMICALS INVESTORS SE - WO2011/149778, 2011, A1 Location in patent: Page/Page column 2; 77; 80

17
[ 34301-54-7 ]
[ 552-89-6 ]
[ 1383611-85-5 ]

Yield	Reaction Conditions	Operation in experiment
95%	With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 16h; Inert atmosphere;	2-thioetherbenzaldehyde general procedure; 2-nitrobenzaldehyde (33 mmol) and K2CO3 (37 mmol) were dissolved in dry DMF (50 ml) under a nitrogen atmosphere. The thiol (35 mmol) was then added at room temp, while stirring at a suitable rate to control the exothermic reaction and the mixture was stirred at 80°C for 16 hour. The mixture was cooled at room temp., ¾0 (200 ml) was added and the mixture was extracted with MTBE/pentane (1:1). The organic layers were washed with aq. sat. NH4CI solution and brine, dried with MgS04, and the solvents were distilled under reduced pressure. The crude product was purified by bulb-to-bulb distillation or column chromatography (Silicagel, Pent/Et20).; 2-(Adamantan- 1 -ylthio)benzaldehyde; Yellow dense oil, 95% yield. .H NMR (400 MHz, CDC13): δ 10.82 (s, 1H), 8.05-7.94 (m, 1H), 7.67-7.47 (m, 3H), 2.06-1.98 (m, 3H), 1.85-1.76 (m, 6H), 1.7-1.53 (m, 6H); 13C NMR (100 MHz, CDC13): δ 193.8 (CH), 140.3 (CH), 139.8 (C), 134.6 (C), 133.4 (CH), 129.5 (CH), 128.0 (CH), 49.7 (C), 43.7 (CH2), 36.0 (CH2), 30.0 (CH).
95%	With potassium carbonate In N,N-dimethyl-formamide at 20 - 80℃; for 16h;

Reference： [1]Current Patent Assignee: Firmenich International SA - WO2012/84810, 2012, A1 Location in patent: Page/Page column 24
[2]Patchett, Ruth; Magpantay, Iris; Saudan, Lionel; Schotes, Christoph; Mezzetti, Antonio; Santoro, Francesco [Angewandte Chemie - International Edition, 2013, vol. 52, # 39, p. 10352 - 10355][Angew. Chem., 2013, vol. 125, # 39, p. 10542 - 10545,4]

18
[ 34301-54-7 ]
[ 139152-08-2 ]
4,5-bis(1-adamantylsulfanyl)pthalonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 20h;	1 (0.591 g, 3.00 mmol) and 2 (1.262 g, 7.50 mmol) were dissolved in DMF (18 mL), next K2CO3 (4.14 g, 30 mmol) was added in two portions and the reaction mixture was stirred for 20 h at room temperature. After that time the reaction mixture was poured into ice-water. The resulting solid was filtered, washed with water, dried, taken into reflux in CH3OH (20 mL) for 30 min in order to remove soluble impurities. Pale yellow amorphous solid (1.370 g, 99%) was obtained. M.p. 219-221 C. Rf = 0.46 (n-hexane:EtOAc 7:1). Anal. Calc. for C28H32N2S2: C, 73.00; H, 7.00; N, 6.08; S, 13.92. Found: C, 72.88; H, 7.00; N, 6.06; S, 14.01.1H NMR (400 MHz, DMSO-d6) delta = 8.15 (s, 2H), 2.02 (bs, 6H), 1.89 (bs, 12H), 1.63 (bs, 12H). 13C NMR (101 MHz, DMSO-d6) delta = 144.8, 139.0, 115.4, 112.8, 52.1, 42.90, 35.3, 29.5. MS (ES) 483 [M+Na]+, 499 [M+K]+.

Reference： [1]Inorganic Chemistry Communications,2013,vol. 27,p. 56 - 59

19
[ 34301-54-7 ]
[ 79544-27-7 ]
[ 1430846-60-8 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-Adamantanethiol With sodium hydride In dimethyl sulfoxide; mineral oil at 20℃; for 0.333333h; Stage #2: 2-bromo-6-fluorobenzonitrile In dimethyl sulfoxide; mineral oil at 130℃; for 1h;	48.48A 2-(tricyclo[3.3.1.13,7]dec-1-ylsulfanyl)-6-bromo-benzonitrile Example 48A 2-(tricyclo[3.3.1.13,7]dec-1-ylsulfanyl)-6-bromo-benzonitrile 1-Adamantanethiol (278 mg) was dissolved in dimethyl sulfoxide (10 mL). Sodium hydride (60% in mineral oil, 42 mg) was added, and the solution was stirred at room temperature for 20 minutes. 2-Bromo-6-fluorobenzonitrile (300 mg) was added and the solution was heated to 130° C. for 1 hour. The solution was cooled, added to diethyl ether, washed with 1 M aqueous HCl three times, washed with brine, and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under vacuum to yield the title compound.

Reference： [1]Current Patent Assignee: POTISEK STEPHANIE L; ABBVIE INC - US2013/96120, 2013, A1 Location in patent: Paragraph 1044

20
[ 34301-54-7 ]
[ 1430847-18-9 ]
[ 1430847-19-0 ]

Yield	Reaction Conditions	Operation in experiment
	With caesium carbonate In N,N-dimethyl acetamide at 120℃; for 2h; Microwave irradiation;	74.74B tert-butyl 6-(8-(benzo[d]thiazol-2-ylcarbamoyl)-3,4-dihydroisoquinolin-2(1H)-yl)-2'-(tricyclo[3.3.1.13,7]dec-1-an-3-ylthio)-3'-methyl-3,4'-bipyridine-2-carboxylate Example 74B tert-butyl 6-(8-(benzo[d]thiazol-2-ylcarbamoyl)-3,4-dihydroisoquinolin-2(1H)-yl)-2'-(tricyclo[3.3.1.13,7]dec-1-an-3-ylthio)-3'-methyl-3,4'-bipyridine-2-carboxylate To a solution of EXAMPLE 74A (130 mg) in N,N-dimethylacetamide (4 mL) was added 1-admantanethiol (111 mg) and Cs2CO3 (215 mg). The mixture was stirred at 120° C. under microwave conditions (Biotage) for 2 hours. The mixture was diluted with ethyl acetate (200 mL) and washed with water and brine and dried over Na2SO4. After filtration and evaporation of the solvent, the crude material was loaded on a column and eluted with 20% ethyl acetate in dichloromethane to provide the title compound.

Reference： [1]Current Patent Assignee: POTISEK STEPHANIE L; ABBVIE INC - US2013/96120, 2013, A1 Location in patent: Paragraph 1147

21
[ 34301-54-7 ]
[ 172876-96-9 ]
[ 39825-84-8 ]

Reference： [1]Chemistry - A European Journal,2015,vol. 21,p. 2662 - 2668

22
D-glucose pentaacetate [ No CAS ]
[ 34301-54-7 ]
1-adamantyl 2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranoside [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With boron trifluoride diethyl etherate In dichloromethane at 0℃; Inert atmosphere; Sealed tube;
64%	With boron trifluoride diethyl etherate In dichloromethane at 0℃; Inert atmosphere;
	With boron trifluoride diethyl etherate In dichloromethane at 0 - 20℃; Inert atmosphere;

Reference： [1]Blaszczyk, Stephanie A.; Xiao, Guozhi; Wen, Peng; Hao, Hua; Wu, Jessica; Wang, Bo; Carattino, Francisco; Li, Ziyuan; Glazier, Daniel A.; McCarty, Bethany J.; Liu, Peng; Tang, Weiping [Angewandte Chemie - International Edition, 2019, vol. 58, # 28, p. 9542 - 9546][Angew. Chem., 2019, vol. 131, # 28, p. 9642 - 9646,5]
[2]Moya-Lpez, Juan Francisco; Elhalem, Eleonora; Recio, Roco; lvarez, Eleuterio; Fernndez, Inmaculada; Khiar, Noureddine [Organic and Biomolecular Chemistry, 2015, vol. 13, # 6, p. 1904 - 1914]
[3]Chu, An-Hsiang Adam; Minciunescu, Andrei; Bennett, Clay S. [Organic Letters, 2015, vol. 17, # 24, p. 6262 - 6265]

23
[ 34301-54-7 ]
[ 623-00-7 ]
4-(adamantan-1-ylthio)benzonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	With tris(2,2-bipyridine)ruthenium(II) hexafluorophosphate; (1,2-dimethoxyethane)dichloronickel(II); diisopropylammonium bis(catecholato)isobutylsilicate; 4,4'-di-tert-butyl-2,2'-bipyridine In N,N-dimethyl-formamide at 27℃; for 40h; Irradiation; Inert atmosphere;

Reference： [1]Jouffroy, Matthieu; Kelly, Christopher B.; Molander, Gary A. [Organic Letters, 2016, vol. 18, # 4, p. 876 - 879]

24
[ 34301-54-7 ]
[ 1459246-62-8 ]
C₂₀H₂₆OS [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
98%	With bis[2-(diphenylphosphino)phenyl] ether; bis(dibenzylideneacetone)-palladium⁽⁰⁾ In acetonitrile at 70℃; for 12h; stereoselective reaction;

Reference： [1]Gómez, José Enrique; Guo, Wusheng; Kleij, Arjan W. [Organic Letters, 2016, vol. 18, # 23, p. 6042 - 6045]

25
[ 34301-54-7 ]
[ 106-93-4 ]
[ 34895-42-6 ]

Yield	Reaction Conditions	Operation in experiment
88%	In methanol at 0 - 20℃; for 16h;
	With potassium hydroxide In methanol at 0℃; for 0.25h;	Preparation of thioether With methanol as solvent,A 1 equivalent of the corresponding dibromoalkane,2.05 equivalents of thiols or thiophenes and 2.1 equivalents of K0H are mixed,0 ° C ice water bath for 15min,Then remove the ice bath,Stir at room temperature overnight;After the reaction is complete,The solvent was removed by steaming,Washed with water to remove potassium bromide,Column (pure petroleum ether) or recrystallized to obtain the corresponding thioether;

Reference： [1]Li, You-Gui; Li, Li; Yang, Ming-Yue; He, Gang; Kantchev, Eric Assen B. [Journal of Organic Chemistry, 2017, vol. 82, # 9, p. 4907 - 4917]
[2]Current Patent Assignee: HEFEI UNIVERSITY OF TECHNOLOGY - CN105130857, 2017, B Location in patent: Paragraph 0014-0015

26
[ 34301-54-7 ]
[ 107-18-6 ]
3-((3s,5s,7s)-adamantan-1-ylthio)propan-1-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	With 10-methyl-9-(2,4,6-trimethylphenyl) acridinium tetrafluoroborate In acetonitrile at 20℃; for 6h; Sealed tube; Microwave irradiation;
77%	With 10-methyl-9-(2,4,6-trimethylphenyl) acridinium tetrafluoroborate In acetonitrile at 20℃; for 6h; Irradiation; Sealed tube;

Reference： [1]Zhao, Gaoyuan; Kaur, Sarbjeet; Wang, Ting [Organic Letters, 2017, vol. 19, # 12, p. 3291 - 3294]
[2]Kaur, Sarbjeet; Zhao, Gaoyuan; Busch, Evan; Wang, Ting [Organic and Biomolecular Chemistry, 2019, vol. 17, # 7, p. 1955 - 1961]

27
[ 34301-54-7 ]
3-(2-(diphenylphosphaneyl)ethyl)oxazolidin-2-one [ No CAS ]
2-diphenylphosphino-N-[2-(1-adamantylthio)ethyl]ethylamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67.5%	With sodium t-butanolate In tert-Amyl alcohol for 1h; Reflux;	7 Example 7) Synthesis of 2-Diphenylphosphino-N-[2-(1-adamantylthio)ethyl]ethylamine (Structural Formula (1^D-4)) (Eq. 13) To a 100 mL four-necked round-bottom flask, a magnetic stirrer bar, a condenser, a thermometer, and a three-way stopcock were attached, and the inside was purged with nitrogen. Then, 3-[2-(diphenylphosphino)ethyl]-2-oxazolidinone (3C-1) (4.2 g, 14.0 mmol, 1.0 equivalents) obtained in Step 1 of Example 2, tAmOH (28 mL), 1-adamantanethiol (5-18) (2.5 g, 14.9 mmol, 1.05 equivalents), and sodium tert-butoxide (NaOtBu) (1.5 g, 15.4 mmol, 1.1 equivalents) were sequentially added, and the obtained suspension was stirred for 1 hour under reflux. After the reaction liquid was cooled to room temperature, water (25 mL) and ethyl acetate (50 mL) were sequentially added, followed by stirring. Then, the mixture was allowed to stand, and the aqueous layer was separated. The organic layer was concentrated under reduced pressure, and then the obtained residue was purified by silica gel column chromatography (eluent: toluene/ethyl acetate/triethylamine=4/1/0.05 to 1/1/0.02) to obtain 4.0 g of title compound (1D-4) as a yellow viscous liquid. Isolated yield: 67.5%. 1H NMR (400 MHz, CDCl3): δ=7.47-7.38 (m, 4H), 7.38-7.28 (m, 6H), 2.79-2.71 (m, 4H), 2.63 (t, J=6.0 Hz, 2H), 2.29-2.24 (m, 2H), 2.03 (br s, 3H), 1.83 (d, J=2.8 Hz, 6H), 1.73-1.62 (m, 6H), 1.52* (br s, 1H). (* note that a peak attributable to water was included) 31P NMR (161 MHz, CDCl3): δ=-20.7.

Reference： [1]Current Patent Assignee: TAKASAGO INTERNATIONAL CORPORATION - US2017/233418, 2017, A1 Location in patent: Paragraph 0244; 0245; 0246; 0247; 0248

28
[ 34301-54-7 ]
C₂₃H₃₃NO₁₄ [ No CAS ]
C₃₁H₄₅NO₁₂S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With boron trifluoride diethyl etherate In dichloromethane at 0 - 20℃; for 12h;	4.3 Example 4 80 g of the compound 2 obtained in the step (2) was dissolved in 160 ml of methylene chloride, and 5.5 g of BF3-Et2O and 2.5 g of 1-adamantanethiol were successively added thereto. The reaction was stirred for 12 hours and then cooled to 0 ° C. 200 ml of saturated sodium bicarbonate The solution was stirred at pH to 8 and the organic phase was distilled to give an oily crude product. The crude oily product was added to 150 ml of ethanol, heated to 40 ° C and then 250 ml of water was added dropwise with stirring. Crystallization for 2 hours, suction filtration, and the cake was recrystallized from petroleum ether to give 85.7 g of compound 3 in 89% yield;

Reference： [1]Current Patent Assignee: JINAN SAM BIOLOGICAL MEDICINE TECH - CN106496290, 2017, A Location in patent: Paragraph 0026; 0027; 0028; 0029

29
[ 108-86-1 ]
[ 34301-54-7 ]
[ 88459-01-2 ]

Yield	Reaction Conditions	Operation in experiment
50%	With tetrakis(tri-p-tolylphosphite)nickel⁽⁰⁾; potassium <i>tert</i>-butylate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; zinc In toluene at 110℃; for 16h; Sealed tube; Inert atmosphere;

Reference： [1]Jones, Kieran D.; Power, Dennis J.; Bierer, Donald; Gericke, Kersten M.; Stewart, Scott G. [Organic Letters, 2018, vol. 20, # 1, p. 208 - 211]

30
[ 34301-54-7 ]
[ 1333403-17-0 ]
3-(2-(((1R,3s)-adamantan-1-yl)thio)ethyl)-1-benzyl-1H-imidazol-3-ium bromide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With sodium hydroxide In acetonitrile at 20℃; for 48h; Schlenk technique; Inert atmosphere;
99%	Stage #1: 1-Adamantanethiol With sodium hydroxide In acetonitrile at 25℃; for 0.5h; Inert atmosphere; Schlenk technique; Stage #2: 1-benzyl-3-(2-bromoethyl)-1H-imidazol-3-ium bromide In acetonitrile at 25℃; for 48h; Inert atmosphere; Schlenk technique;

Reference： [1]Egly, Julien; Bouché, Mathilde; Chen, Weighang; Maisse-François, Aline; Achard, Thierry; Bellemin-Laponnaz, Stéphane [European Journal of Inorganic Chemistry, 2018, vol. 2018, # 2, p. 159 - 166]
[2]Achard, Thierry; Bellemin-Laponnaz, Stéphane; Chen, Weiguang; Egly, Julien; Maisse-Francois, Aline; Poblador-Bahamonde, Amalia I. [Dalton Transactions, 2020, vol. 49, # 10, p. 3243 - 3252]

31
[ 34301-54-7 ]
[ 71412-50-5 ]
C₃₀H₄₅Cl₂Rh₂S⁽¹⁺⁾*BF₄^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
63%	Stage #1: 1-Adamantanethiol With sodium hydride In tetrahydrofuran at 20℃; for 12h; Inert atmosphere; Stage #2: [Rh2(η-pentamethylcyclopentadienyl)2Cl3]BF4 In dichloromethane at -78 - 20℃; Inert atmosphere;

Reference： [1]Zhao, Xiangyu; Yang, Dawei; Zhang, Yahui; Wang, Baomin; Qu, Jingping [Organic Letters, 2018, vol. 20, # 17, p. 5357 - 5361]

32
[ 34301-54-7 ]
[ 130-61-0 ]
2-((adamantan-1-yl)thio)-10-(2-(1-methylpiperidin-2-yl)ethyl)-10H-phenothiazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
61%	With Singacycle A1; lithium hexamethyldisilazane; In o-xylene; at 160℃; for 12h;Glovebox; Sealed tube;	In the glovebox, thioridazine (0.2 mmol), 1-adamentanethiol (2.0 equiv, 0.4 mmol),LiHMDS (3.6 equiv), and SingaCycle Al (0.4 mol%) were added into an oven-dried 8 ml vial with a magnetic stirring bar, followed by addition of o-xylene (1 .0 ml). The vial was sealed and removed out of the glovebox and heated to 160 00. After 12 h, the vial was cooled to room temperature. The reaction was diluted with ethyl acetate and washed with NaOH solution. The aqueous phase was extractedwith ethyl acetate 3 times. The collected organic phases were dried over anhydrous Na2SO4. The solvent was removed under reduced pressure and the residue was purified by flash column chromatography (0-5% MeOH in DCM) to give the title product. Isolated as syrup like liquid (59.4 mg, 61%). 1H NMR (500 MHz, Chloroform-d) 6 7.20-7.11 (m, 2H), 7.08-7.03 (m, 2H), 6.98 (d, J = 1 .3 Hz,1H), 6.97-6.87 (m, 2H), 3.98 (ddd, J= 13.6, 8.2, 5.2 Hz, 1H), 3.87 (ddd, J 14.2,8.2, 6.6 Hz, 1H), 3.00-2.82 (m, 1H), 2.52-2.18 (m, 6H), 2.07-1.98 (m, 3H), 1.97-1.86 (m, 1H), 1.80 (d, J= 2.8 Hz, 6H), 1.74-1.71 (m, 2H), 1.69-1.52 (m, 8H), 1.54-1.47 (m, 1H), 1.37-1.17 (m, 1H). 130 NMR (126 MHz, ODd3) 6 144.9, 131.7,129.5, 127.6, 127.5, 127.4, 126.9, 126.6, 125.0, 124.4, 122.8, 115.8, 62.2, 56.7,48.2, 43.9, 43.7, 42.5, 36.1, 30.2, 30.0, 29.4, 25.1, 23.7. HRMS 030H38S2N2 [M-H] +calculated 491 .2549, found: 491.2552.

Reference： [1]Patent: WO2018/162364,2018,A1 .Location in patent: Page/Page column 31; 32

33
sodium hexafluoroantimonate [ No CAS ]
[ 34301-54-7 ]
gold(III) tetrachloride trihydrate [ No CAS ]
[ 14866-33-2 ]
silver nitrate [ No CAS ]
[ 2071-20-7 ]
Au₉Ag₁₂⁽¹³⁺⁾*6C₂₅H₂₂P₂*6Br^(1-)*4C₁₀H₁₅S^(1-)*3F₆Sb^(1-) [ No CAS ]

Reference： [1]Inorganic Chemistry,2018,vol. 57,p. 5114 - 5119

34
[ 34301-54-7 ]
C₅₇H₇₇IN₄O₂₂S₄ [ No CAS ]
C₆₆H₈₉IN₄O₂₂S₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With triethylamine In N,N-dimethyl-formamide; acetonitrile at -15℃; for 0.783333h;	5-10 A solution of 8 (4.50 mg, 3.16 mitioI, 1.00 equiv.) in DMF (69.2 pL) was diluted with MeCN (1.0 mL) and the resulting light yellow solution was cooled to -15 °C and a solution of 1- adamantanethiol (5.30 mg, 31.6 mitioI, 10.0 equiv.) in MeCN (53.1 pL), followed by Et3N (4.40 pL, 31.6 mitioI, 10.0 equiv.). The resulting light yellow suspension was left in -15 °C for 47 minutes and was then allowed to warm to rt. After circa 50 minutes at rt the reaction mixture was cone in vacuo and purified by silica chromatography (0 25% MeOH in DCM). The desired product was obtained as an off-white residue (3.3 mg, 2.2 pmol, 70% yield). LCMS (ESI+) calculated for C66Hg0IN4O22S3+ (M+H+) 1513.42, found 1513.45.

Reference： [1]Current Patent Assignee: SYNAFFIX BV - WO2019/110725, 2019, A1 Location in patent: Paragraph 0279; 0282

35
[ 34301-54-7 ]
2-(4-cyanobenzyl)-1-methoxypersulfide [ No CAS ]
C₁₈H₂₁NS₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With tris(pentafluorophenyl)borate In dichloromethane at 20℃; for 5h; Inert atmosphere; Green chemistry;	13 Synthesis of Compound 3l: Under a nitrogen atmosphere, 1a (42.3 mg, 0.2 mmol), 1-adamantanethiol 2l (37.0 mg, 0.22 mmol), B(C6F5)3 (2.6 mg, 0.005 mmol), dichloromethane (2.0 mL) were equentially added to the reaction tube, the reaction system was stirred at room temperature for 5 hours. After the reaction is completed, dilute with dichloromethane to remove the solvent. Column chromatography gave white solid compound 3l (62.2 mg, 89%)

Reference： [1]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN110117239, 2019, A Location in patent: Paragraph 0099-0102

36
[ 34301-54-7 ]
[ 88043-21-4 ]
(2S,4S)-1-tert-butyl-2-methyl-4-(adamantan-1-ylthio)-pyrrolidine-1,2-dicarboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	With sodium hydride; In N,N-dimethyl-formamide; mineral oil; at -20 - 0℃; for 69h;Inert atmosphere; Schlenk technique;	Sodium hydride (0.050 g, 2.065 mmol) was placed in a 50 mL Schlenk flask and was suspended in 11 mL of anhydrous DMF, under an argon atmosphere. A solution of 1-adamantanethiol 95% (0.366 g, 2.065 mmol) in DMF (11 mL) was added via cannula to the suspension of sodium hydride at -20 C under argon. The mixture was stirred for 20 minutes and a solution of 16 (0.750 g, 1.878 mmol) in DMF (11 mL) was added via cannula to the mixture. Stirring was continued at -20 C for one hour and then the temperature was raised to 0 C. Stirring was continued at that temperature for 68 hours. Methanol (20 mL) was added and then brine (60 mL) and the reaction mixture was extracted with hexane (3 70 mL). The organic layers were washed once with water, dried with andydrous MgSO4 and the solvent was removed under reduced pressure. The crude product was purified by flash column chromatography over silica gel, using hexane/ethyl acetate mixtures (9:1 first to separate the unreacted thiol and then 8:2) as eluant. The title product 17 (0.604 g, 81% yield) was obtained as a colourless oil; Found C 63.71, H 8.21, N 3.63, S 8.15. C21H33NO4S requires C 63.76, H 8.41, N 3.54, S 8.11%; []D27 = -59.6 (c = 1.21 in CHCl3 ); 1H NMR (400 MHz, CDCl3): delta 4.24 (m, 1H), 4.07- 3.79 (m, 1H), 3.72 (s, 3H, OCH3), 3.37 - 3.24 (m, 1H), 3.20 (m, 1H), 2.68 - 2.52 (m, 1H), 2.04 (s, 3H, 3 × CH adamantyl), 1.86 (s, 7H, 3 × CH2 adamantyl), 1.69 (s, 6H, 3 × CH2 adamantyl), 1.43 ppm (m, 9H, 3 × CH3-Boc); 13C NMR (101 MHz, CDCl3, rotamers are detected in the spectra) delta 173.16, 172.89 (COOH), 153.35 (N-C=O), 80.51 (C), 58.87 (CH), 54.38 (CH2), 52.43, 52.26 (CH3), 45.62 (C), 44.26 (CH2), 39.21 (CH2), 36.36 (CH2), 35.82 (CH), 29.91 (CH), 28.61, 28.47 ppm (CH3); IR (ATR): nu 2976, 2904, 2849, 1750, 1700, 1477, 1450, 1392, 1366, 1254, 1177, 1116, 1043 cm-1; HRMS (TOF MS ES+): m/z calcd for C21H33NO4NaS+: 418.2023 [M+Na+]; found 418.203.

Reference： [1]Tetrahedron,2019,vol. 75

37
[ 34301-54-7 ]
[ 100-41-4 ]
((1s,3s)-adamantan-1-yl)(1-phenylethyl)sulfane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
24%	With N-Bromosuccinimide; di-tert-butyl peroxide; nickel(II) acetate tetrahydrate; 2,2'-Bipyrimidine In fluorobenzene at 120℃; for 24h; Inert atmosphere;	21 Example 21 The preparation of (1-phenylethyl) (1-adamantyl) sulfide 3au is as follows: Under nitrogen protection,Add 1-adamantyl mercaptan 2u (0.5 mmol), Ni (OAc) 2.4H2O (0.025 mmol),2,2’-bipyrimidine (0.025 mmol), NBS (0.025 mmol), TBP (0.5 mmol),Ethylbenzene 1a (15 mmol) and fluorobenzene (0.5 mL) were added to the reaction tube.Stir at 120 ° C for 24 hours. After stopping the reaction, cool to room temperature, evaporate the solvent,Column chromatography, the volume ratio (mL / mL) of the eluent used is ethyl acetate: petroleum ether = 0: 100 ~ 1: 100,(1-Phenyl) (1-adamantyl) sulfide 3au was obtained in a yield of 24%.
21%	With N-Bromosuccinimide; di-tert-butyl peroxide; Bathocuproine; nickel(II) acetate tetrahydrate at 140℃; for 24h; Inert atmosphere; Schlenk technique;	3. General procedure for the oxidative dehydrogenative coupling reaction General procedure: Under nitrogen atmosphere, Ni(OAc)2*4H2O (6.2 mg, 0.025 mmol, 5 mol %), BC (11.0 mg, 0.03 mmol, 6 mol %), B1 (62.0 mg, 0.5 mmol, 1 equiv), DTBP (92.0 μL, 0.5 mmol, 1 equiv) and A1 (1.8 mL, 15 mmol, 30 equiv) were added into the reaction tube, and the mixture was stirred at 140 °C for 24 hours. After cooling to room temperature, the solvent was removed under reduced pressure. Then, the reaction mixture was purified by flash column chromatography on silica gel and eluted with petroleum ether to give the desired product 1.

Reference： [1]Current Patent Assignee: CHINESE ACADEMY OF SCIENCES - CN110483349, 2019, A Location in patent: Paragraph 0039
[2]Liu, Shengping; Jin, Shengnan; Wang, Hao; Qi, Zaojuan; Hu, Xiaoxue; Qian, Bo; Huang, Hanmin [Tetrahedron Letters, 2021, vol. 68]

38
[ 34301-54-7 ]
[ 387-45-1 ]
2-(1-adamantylsulfanyl)-6-chlorobenzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	Stage #1: 1-Adamantanethiol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 1.5h; Inert atmosphere; Stage #2: 2-chloro-6-fluorobenzaldehyde In N,N-dimethyl-formamide; mineral oil at -40℃; for 2h; Inert atmosphere;	Typical procedure for the preparation of compounds 2. General procedure: To a suspension of NaH (592 mg, ca. 60%in mineral oil, washed with hexane, ca. 15 mmol) in N,N-dimethylformamide (DMF, 13 mL) was added1-adamantanethiol (2.17 g, 12.9 mmol) in DMF (20 mL) at 0 °C under N2. The reaction mixture wasstirred at 0 °C for 1.5 h, and a solution of 1a (2.97 g, 10.5 mmol) in DMF (20 mL) was added at -40 °C.The reaction mixture was stirred at -40 °C for 2 h. The reaction mixture was poured into water, andextracted with EtOAc. The organic layer was washed with brine and dried over MgSO4. The filtratewas concentrated under reduced pressure, and purified by silica gel column chromatography(hexane-EtOAc, 4:1) to give 4.27 g (9.93 mmol) of 2a.

Reference： [1]Toyota, Kozo; Mutoh, Hirotaka; Kishi, Hiroki; Mikami, Shinichi; Tanaka, Hiroki; Yoshida, Shuhei; Naganuma, Daisuke [Heterocycles, 2019, vol. 98, # 10, p. 1355 - 1374]

39
[ 34301-54-7 ]
[ 85070-48-0 ]
2-(1-adamantylsulfanyl)-3-chlorobenzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%		General procedure: To a suspension of NaH (592 mg, ca. 60%in mineral oil, washed with hexane, ca. 15 mmol) in N,N-dimethylformamide (DMF, 13 mL) was added1-adamantanethiol (2.17 g, 12.9 mmol) in DMF (20 mL) at 0 C under N2. The reaction mixture wasstirred at 0 C for 1.5 h, and a solution of 1a (2.97 g, 10.5 mmol) in DMF (20 mL) was added at -40 C.The reaction mixture was stirred at -40 C for 2 h. The reaction mixture was poured into water, andextracted with EtOAc. The organic layer was washed with brine and dried over MgSO4. The filtratewas concentrated under reduced pressure, and purified by silica gel column chromatography(hexane-EtOAc, 4:1) to give 4.27 g (9.93 mmol) of 2a.

Reference： [1]Heterocycles,2019,vol. 98,p. 1355 - 1374

40
[ 34301-54-7 ]
[ 446-52-6 ]
[ 1383611-85-5 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-Adamantanethiol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 1.5h; Inert atmosphere; Stage #2: 2-Fluorobenzaldehyde In N,N-dimethyl-formamide; mineral oil at -40℃; for 2h; Inert atmosphere;	Typical procedure for the preparation of compounds 2. General procedure: To a suspension of NaH (592 mg, ca. 60%in mineral oil, washed with hexane, ca. 15 mmol) in N,N-dimethylformamide (DMF, 13 mL) was added1-adamantanethiol (2.17 g, 12.9 mmol) in DMF (20 mL) at 0 °C under N2. The reaction mixture wasstirred at 0 °C for 1.5 h, and a solution of 1a (2.97 g, 10.5 mmol) in DMF (20 mL) was added at -40 °C.The reaction mixture was stirred at -40 °C for 2 h. The reaction mixture was poured into water, andextracted with EtOAc. The organic layer was washed with brine and dried over MgSO4. The filtratewas concentrated under reduced pressure, and purified by silica gel column chromatography(hexane-EtOAc, 4:1) to give 4.27 g (9.93 mmol) of 2a.

Reference： [1]Toyota, Kozo; Mutoh, Hirotaka; Kishi, Hiroki; Mikami, Shinichi; Tanaka, Hiroki; Yoshida, Shuhei; Naganuma, Daisuke [Heterocycles, 2019, vol. 98, # 10, p. 1355 - 1374]

41
[ 34301-54-7 ]
2-fluoro-3,6-diiodobenzaldehyde [ No CAS ]
2-(1-adamantylsulfanyl)-3,6-diiodobenzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84%	Stage #1: 1-Adamantanethiol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 1.5h; Inert atmosphere; Stage #2: 2-fluoro-3,6-diiodobenzaldehyde In N,N-dimethyl-formamide; mineral oil at -40℃; for 2h; Inert atmosphere;	Typical procedure for the preparation of compounds 2. General procedure: To a suspension of NaH (592 mg, ca. 60%in mineral oil, washed with hexane, ca. 15 mmol) in N,N-dimethylformamide (DMF, 13 mL) was added1-adamantanethiol (2.17 g, 12.9 mmol) in DMF (20 mL) at 0 °C under N2. The reaction mixture wasstirred at 0 °C for 1.5 h, and a solution of 1a (2.97 g, 10.5 mmol) in DMF (20 mL) was added at -40 °C.The reaction mixture was stirred at -40 °C for 2 h. The reaction mixture was poured into water, andextracted with EtOAc. The organic layer was washed with brine and dried over MgSO4. The filtratewas concentrated under reduced pressure, and purified by silica gel column chromatography(hexane-EtOAc, 4:1) to give 4.27 g (9.93 mmol) of 2a.

Reference： [1]Toyota, Kozo; Mutoh, Hirotaka; Kishi, Hiroki; Mikami, Shinichi; Tanaka, Hiroki; Yoshida, Shuhei; Naganuma, Daisuke [Heterocycles, 2019, vol. 98, # 10, p. 1355 - 1374]

42
[ 34301-54-7 ]
3,6-dichloro-2-fluorobenzaldehyde [ No CAS ]
2-(1-adamantylsulfanyl)-3,6-dichlorobenzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
64%	Stage #1: 1-Adamantanethiol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 1.5h; Inert atmosphere; Stage #2: 3,6-dichloro-2-fluorobenzaldehyde In N,N-dimethyl-formamide; mineral oil at -40℃; for 2h; Inert atmosphere;	Typical procedure for the preparation of compounds 2. General procedure: To a suspension of NaH (592 mg, ca. 60%in mineral oil, washed with hexane, ca. 15 mmol) in N,N-dimethylformamide (DMF, 13 mL) was added1-adamantanethiol (2.17 g, 12.9 mmol) in DMF (20 mL) at 0 °C under N2. The reaction mixture wasstirred at 0 °C for 1.5 h, and a solution of 1a (2.97 g, 10.5 mmol) in DMF (20 mL) was added at -40 °C.The reaction mixture was stirred at -40 °C for 2 h. The reaction mixture was poured into water, andextracted with EtOAc. The organic layer was washed with brine and dried over MgSO4. The filtratewas concentrated under reduced pressure, and purified by silica gel column chromatography(hexane-EtOAc, 4:1) to give 4.27 g (9.93 mmol) of 2a.

Reference： [1]Toyota, Kozo; Mutoh, Hirotaka; Kishi, Hiroki; Mikami, Shinichi; Tanaka, Hiroki; Yoshida, Shuhei; Naganuma, Daisuke [Heterocycles, 2019, vol. 98, # 10, p. 1355 - 1374]

43
[ 34301-54-7 ]
3-bromo-2-fluoro-6-iodobenzaldehyde [ No CAS ]
2-(1-adamantylsulfanyl)-3-bromo-6-iodobenzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	Stage #1: 1-Adamantanethiol With sodium hydride In hexane; N,N-dimethyl-formamide at 0℃; for 0.25h; Inert atmosphere; Stage #2: 3-bromo-2-fluoro-6-iodobenzaldehyde In tetrahydrofuran; hexane; N,N-dimethyl-formamide at -15℃;	2-(1-Adamantylsulfanyl)-3-bromo-6-iodobenzaldehyde (6g) General procedure: NaH (0.3687 g, ca. 60% in mineral oil, ca. 9.2 mmol) was washed with hexane under nitrogen atmosphere. 1-Adamantanethiol (1.5670 g, 9.218 mmol) in DMF (15 mL) was slowly added to the NaH at 0 °C and the reaction mixture was stirred at 0 °C for 15 min. After cooling the mixture to -40 °C, 1b (1.9756 g, 8.320 mmol) in THF (8 mL) was added and the resulting mixture was stirred at -40 °C for 6 h then warmed to room temperature. The solution was poured into a saturated aqueous NaCl solution (brine), then worked up with a hexane-AcOEt (4:1) solution. The organic phase was separated, dried over Na2SO4, and the solvent was removed under reduced pressure. Silica gel column chromatographic treatment of the residue (hexane-CHCl3 7:3)afforded 6b (2.7929 g, 7.240 mmol, 87% yield); a pale yellow solid
	Stage #1: 1-Adamantanethiol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 1.5h; Inert atmosphere; Stage #2: 3-bromo-2-fluoro-6-iodobenzaldehyde In N,N-dimethyl-formamide; mineral oil at -40℃; for 2h; Inert atmosphere;	Typical procedure for the preparation of compounds 2. General procedure: To a suspension of NaH (592 mg, ca. 60%in mineral oil, washed with hexane, ca. 15 mmol) in N,N-dimethylformamide (DMF, 13 mL) was added1-adamantanethiol (2.17 g, 12.9 mmol) in DMF (20 mL) at 0 °C under N2. The reaction mixture wasstirred at 0 °C for 1.5 h, and a solution of 1a (2.97 g, 10.5 mmol) in DMF (20 mL) was added at -40 °C.The reaction mixture was stirred at -40 °C for 2 h. The reaction mixture was poured into water, andextracted with EtOAc. The organic layer was washed with brine and dried over MgSO4. The filtratewas concentrated under reduced pressure, and purified by silica gel column chromatography(hexane-EtOAc, 4:1) to give 4.27 g (9.93 mmol) of 2a.

Reference： [1]Kishi, Hiroki; Mikami, Shinichi; Tanaka, Hiroki; Toyota, Kozo; Yoshida, Shuhei [Heterocycles, 2018, vol. 96, # 9, p. 1529 - 1548]
[2]Toyota, Kozo; Mutoh, Hirotaka; Kishi, Hiroki; Mikami, Shinichi; Tanaka, Hiroki; Yoshida, Shuhei; Naganuma, Daisuke [Heterocycles, 2019, vol. 98, # 10, p. 1355 - 1374]

44
[ 34301-54-7 ]
3-chloro-2-fluoro-6-iodobenzaldehyde [ No CAS ]
2-(1-adamantylsulfanyl)-3-chloro-6-iodobenzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84%	Stage #1: 1-Adamantanethiol With sodium hydride In hexane; N,N-dimethyl-formamide at 0℃; for 0.25h; Inert atmosphere; Stage #2: 3-chloro-2-fluoro-6-iodobenzaldehyde In tetrahydrofuran; hexane; N,N-dimethyl-formamide at -63℃;	2-(1-Adamantylsulfanyl)-3-chloro-6-iodobenzaldehyde (6f) General procedure: NaH (0.3687 g, ca. 60% in mineral oil, ca. 9.2 mmol) was washed with hexane under nitrogen atmosphere. 1-Adamantanethiol (1.5670 g, 9.218 mmol) in DMF (15 mL) was slowly added to the NaH at 0 °C and the reaction mixture was stirred at 0 °C for 15 min. After cooling the mixture to -40 °C, 1b (1.9756 g, 8.320 mmol) in THF (8 mL) was added and the resulting mixture was stirred at -40 °C for 6 h then warmed to room temperature. The solution was poured into a saturated aqueous NaCl solution (brine), then worked up with a hexane-AcOEt (4:1) solution. The organic phase was separated, dried over Na2SO4, and the solvent was removed under reduced pressure. Silica gel column chromatographic treatment of the residue (hexane-CHCl3 7:3)afforded 6b (2.7929 g, 7.240 mmol, 87% yield); a pale yellow solid
	Stage #1: 1-Adamantanethiol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 1.5h; Inert atmosphere; Stage #2: 3-chloro-2-fluoro-6-iodobenzaldehyde In N,N-dimethyl-formamide; mineral oil at -40℃; for 2h; Inert atmosphere;	Typical procedure for the preparation of compounds 2. General procedure: To a suspension of NaH (592 mg, ca. 60%in mineral oil, washed with hexane, ca. 15 mmol) in N,N-dimethylformamide (DMF, 13 mL) was added1-adamantanethiol (2.17 g, 12.9 mmol) in DMF (20 mL) at 0 °C under N2. The reaction mixture wasstirred at 0 °C for 1.5 h, and a solution of 1a (2.97 g, 10.5 mmol) in DMF (20 mL) was added at -40 °C.The reaction mixture was stirred at -40 °C for 2 h. The reaction mixture was poured into water, andextracted with EtOAc. The organic layer was washed with brine and dried over MgSO4. The filtratewas concentrated under reduced pressure, and purified by silica gel column chromatography(hexane-EtOAc, 4:1) to give 4.27 g (9.93 mmol) of 2a.

Reference： [1]Kishi, Hiroki; Mikami, Shinichi; Tanaka, Hiroki; Toyota, Kozo; Yoshida, Shuhei [Heterocycles, 2018, vol. 96, # 9, p. 1529 - 1548]
[2]Toyota, Kozo; Mutoh, Hirotaka; Kishi, Hiroki; Mikami, Shinichi; Tanaka, Hiroki; Yoshida, Shuhei; Naganuma, Daisuke [Heterocycles, 2019, vol. 98, # 10, p. 1355 - 1374]

45
[ 34301-54-7 ]
C₇H₃BrFIO [ No CAS ]
2-(1-adamantylsulfanyl)-6-bromo-3-iodobenzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
64%	Stage #1: 1-Adamantanethiol With sodium hydride In hexane; N,N-dimethyl-formamide at 0℃; for 0.25h; Inert atmosphere; Stage #2: C₇H₃BrFIO In tetrahydrofuran; hexane; N,N-dimethyl-formamide at -40℃;	2-(1-Adamantylsulfanyl)-6-bromo-3-iodobenzaldehyde (6c) General procedure: NaH (0.3687 g, ca. 60% in mineral oil, ca. 9.2 mmol) was washed with hexane under nitrogen atmosphere. 1-Adamantanethiol (1.5670 g, 9.218 mmol) in DMF (15 mL) was slowly added to the NaH at 0 °C and the reaction mixture was stirred at 0 °C for 15 min. After cooling the mixture to -40 °C, 1b (1.9756 g, 8.320 mmol) in THF (8 mL) was added and the resulting mixture was stirred at -40 °C for 6 h then warmed to room temperature. The solution was poured into a saturated aqueous NaCl solution (brine), then worked up with a hexane-AcOEt (4:1) solution. The organic phase was separated, dried over Na2SO4, and the solvent was removed under reduced pressure. Silica gel column chromatographic treatment of the residue (hexane-CHCl3 7:3)afforded 6b (2.7929 g, 7.240 mmol, 87% yield); a pale yellow solid
	Stage #1: 1-Adamantanethiol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 1.5h; Inert atmosphere; Stage #2: C₇H₃BrFIO In N,N-dimethyl-formamide; mineral oil at -40℃; for 2h; Inert atmosphere;	Typical procedure for the preparation of compounds 2. General procedure: To a suspension of NaH (592 mg, ca. 60%in mineral oil, washed with hexane, ca. 15 mmol) in N,N-dimethylformamide (DMF, 13 mL) was added1-adamantanethiol (2.17 g, 12.9 mmol) in DMF (20 mL) at 0 °C under N2. The reaction mixture wasstirred at 0 °C for 1.5 h, and a solution of 1a (2.97 g, 10.5 mmol) in DMF (20 mL) was added at -40 °C.The reaction mixture was stirred at -40 °C for 2 h. The reaction mixture was poured into water, andextracted with EtOAc. The organic layer was washed with brine and dried over MgSO4. The filtratewas concentrated under reduced pressure, and purified by silica gel column chromatography(hexane-EtOAc, 4:1) to give 4.27 g (9.93 mmol) of 2a.

Reference： [1]Kishi, Hiroki; Mikami, Shinichi; Tanaka, Hiroki; Toyota, Kozo; Yoshida, Shuhei [Heterocycles, 2018, vol. 96, # 9, p. 1529 - 1548]
[2]Toyota, Kozo; Mutoh, Hirotaka; Kishi, Hiroki; Mikami, Shinichi; Tanaka, Hiroki; Yoshida, Shuhei; Naganuma, Daisuke [Heterocycles, 2019, vol. 98, # 10, p. 1355 - 1374]

46
[ 34301-54-7 ]
6-chloro-2-fluoro-3-iodobenzaldehyde [ No CAS ]
2-(1-adamantylsulfanyl)-6-chloro-3-iodobenzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	Stage #1: 1-Adamantanethiol With sodium hydride In hexane; N,N-dimethyl-formamide at 0℃; for 0.25h; Inert atmosphere; Stage #2: 6-chloro-2-fluoro-3-iodobenzaldehyde In tetrahydrofuran; hexane; N,N-dimethyl-formamide at -63℃;	2-(1-Adamantylsulfanyl)-6-chloro-3-iodobenzaldehyde (6e) General procedure: NaH (0.3687 g, ca. 60% in mineral oil, ca. 9.2 mmol) was washed with hexane under nitrogen atmosphere. 1-Adamantanethiol (1.5670 g, 9.218 mmol) in DMF (15 mL) was slowly added to the NaH at 0 °C and the reaction mixture was stirred at 0 °C for 15 min. After cooling the mixture to -40 °C, 1b (1.9756 g, 8.320 mmol) in THF (8 mL) was added and the resulting mixture was stirred at -40 °C for 6 h then warmed to room temperature. The solution was poured into a saturated aqueous NaCl solution (brine), then worked up with a hexane-AcOEt (4:1) solution. The organic phase was separated, dried over Na2SO4, and the solvent was removed under reduced pressure. Silica gel column chromatographic treatment of the residue (hexane-CHCl3 7:3)afforded 6b (2.7929 g, 7.240 mmol, 87% yield); a pale yellow solid
	Stage #1: 1-Adamantanethiol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 1.5h; Inert atmosphere; Stage #2: 6-chloro-2-fluoro-3-iodobenzaldehyde In N,N-dimethyl-formamide; mineral oil at -40℃; for 2h; Inert atmosphere;	Typical procedure for the preparation of compounds 2. General procedure: To a suspension of NaH (592 mg, ca. 60%in mineral oil, washed with hexane, ca. 15 mmol) in N,N-dimethylformamide (DMF, 13 mL) was added1-adamantanethiol (2.17 g, 12.9 mmol) in DMF (20 mL) at 0 °C under N2. The reaction mixture wasstirred at 0 °C for 1.5 h, and a solution of 1a (2.97 g, 10.5 mmol) in DMF (20 mL) was added at -40 °C.The reaction mixture was stirred at -40 °C for 2 h. The reaction mixture was poured into water, andextracted with EtOAc. The organic layer was washed with brine and dried over MgSO4. The filtratewas concentrated under reduced pressure, and purified by silica gel column chromatography(hexane-EtOAc, 4:1) to give 4.27 g (9.93 mmol) of 2a.

Reference： [1]Kishi, Hiroki; Mikami, Shinichi; Tanaka, Hiroki; Toyota, Kozo; Yoshida, Shuhei [Heterocycles, 2018, vol. 96, # 9, p. 1529 - 1548]
[2]Toyota, Kozo; Mutoh, Hirotaka; Kishi, Hiroki; Mikami, Shinichi; Tanaka, Hiroki; Yoshida, Shuhei; Naganuma, Daisuke [Heterocycles, 2019, vol. 98, # 10, p. 1355 - 1374]

47
[ 34301-54-7 ]
[ 1114809-02-7 ]
2-(1-Adamantylsulfanyl)-6-bromo-3-chlorobenzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		General procedure: To a suspension of NaH (592 mg, ca. 60%in mineral oil, washed with hexane, ca. 15 mmol) in N,N-dimethylformamide (DMF, 13 mL) was added1-adamantanethiol (2.17 g, 12.9 mmol) in DMF (20 mL) at 0 C under N2. The reaction mixture wasstirred at 0 C for 1.5 h, and a solution of 1a (2.97 g, 10.5 mmol) in DMF (20 mL) was added at -40 C.The reaction mixture was stirred at -40 C for 2 h. The reaction mixture was poured into water, andextracted with EtOAc. The organic layer was washed with brine and dried over MgSO4. The filtratewas concentrated under reduced pressure, and purified by silica gel column chromatography(hexane-EtOAc, 4:1) to give 4.27 g (9.93 mmol) of 2a.

Reference： [1]Heterocycles,2019,vol. 98,p. 1355 - 1374

48
[ 34301-54-7 ]
[ 1114809-02-7 ]
2-(1-Adamantylsulfanyl)-4-bromo-1-chloro-3-(ethynyl)benzene [ No CAS ]

Reference： [1]Heterocycles,2019,vol. 98,p. 1355 - 1374

49
[ 886615-30-1 ]
[ 34301-54-7 ]
2-(1-adamantylsulfanyl)-3-bromo-6-chlorobenzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	Stage #1: 1-Adamantanethiol With sodium hydride In hexane; N,N-dimethyl-formamide at 0℃; for 0.25h; Inert atmosphere; Stage #2: 3-bromo- 6-chloro-2-fluorobenzaldehyde In tetrahydrofuran; hexane; N,N-dimethyl-formamide at -78℃;	2-(1-Adamantylsulfanyl)-3-bromo-6-chlorobenzaldehyde (6d) General procedure: NaH (0.3687 g, ca. 60% in mineral oil, ca. 9.2 mmol) was washed with hexane under nitrogen atmosphere. 1-Adamantanethiol (1.5670 g, 9.218 mmol) in DMF (15 mL) was slowly added to the NaH at 0 °C and the reaction mixture was stirred at 0 °C for 15 min. After cooling the mixture to -40 °C, 1b (1.9756 g, 8.320 mmol) in THF (8 mL) was added and the resulting mixture was stirred at -40 °C for 6 h then warmed to room temperature. The solution was poured into a saturated aqueous NaCl solution (brine), then worked up with a hexane-AcOEt (4:1) solution. The organic phase was separated, dried over Na2SO4, and the solvent was removed under reduced pressure. Silica gel column chromatographic treatment of the residue (hexane-CHCl3 7:3)afforded 6b (2.7929 g, 7.240 mmol, 87% yield); a pale yellow solid
	Stage #1: 1-Adamantanethiol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 1.5h; Inert atmosphere; Stage #2: 3-bromo- 6-chloro-2-fluorobenzaldehyde In N,N-dimethyl-formamide; mineral oil at -40℃; for 2h; Inert atmosphere;	Typical procedure for the preparation of compounds 2. General procedure: To a suspension of NaH (592 mg, ca. 60%in mineral oil, washed with hexane, ca. 15 mmol) in N,N-dimethylformamide (DMF, 13 mL) was added1-adamantanethiol (2.17 g, 12.9 mmol) in DMF (20 mL) at 0 °C under N2. The reaction mixture wasstirred at 0 °C for 1.5 h, and a solution of 1a (2.97 g, 10.5 mmol) in DMF (20 mL) was added at -40 °C.The reaction mixture was stirred at -40 °C for 2 h. The reaction mixture was poured into water, andextracted with EtOAc. The organic layer was washed with brine and dried over MgSO4. The filtratewas concentrated under reduced pressure, and purified by silica gel column chromatography(hexane-EtOAc, 4:1) to give 4.27 g (9.93 mmol) of 2a.

Reference： [1]Kishi, Hiroki; Mikami, Shinichi; Tanaka, Hiroki; Toyota, Kozo; Yoshida, Shuhei [Heterocycles, 2018, vol. 96, # 9, p. 1529 - 1548]
[2]Toyota, Kozo; Mutoh, Hirotaka; Kishi, Hiroki; Mikami, Shinichi; Tanaka, Hiroki; Yoshida, Shuhei; Naganuma, Daisuke [Heterocycles, 2019, vol. 98, # 10, p. 1355 - 1374]

50
[ 870703-68-7 ]
[ 34301-54-7 ]
2-(1-adamantylsulfanyl)-3,6-dibromobenzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	Stage #1: 1-Adamantanethiol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 1.5h; Inert atmosphere; Stage #2: 3,6-dibromo-2-fluorobenzaldehyde In N,N-dimethyl-formamide; mineral oil at -40℃; for 2h; Inert atmosphere;	Typical procedure for the preparation of compounds 2. To a suspension of NaH (592 mg, ca. 60%in mineral oil, washed with hexane, ca. 15 mmol) in N,N-dimethylformamide (DMF, 13 mL) was added1-adamantanethiol (2.17 g, 12.9 mmol) in DMF (20 mL) at 0 °C under N2. The reaction mixture wasstirred at 0 °C for 1.5 h, and a solution of 1a (2.97 g, 10.5 mmol) in DMF (20 mL) was added at -40 °C.The reaction mixture was stirred at -40 °C for 2 h. The reaction mixture was poured into water, andextracted with EtOAc. The organic layer was washed with brine and dried over MgSO4. The filtratewas concentrated under reduced pressure, and purified by silica gel column chromatography(hexane-EtOAc, 4:1) to give 4.27 g (9.93 mmol) of 2a.2-(1-Adamantylsulfanyl)-3,6-dibromobenzaldehyde (2a): 95% yield; a pale yellow solid; mp92-94 °C; 1H NMR (400 MHz, CDCl3) 1.61 (6H, s, Ad), 1.87 (6H, s, Ad), 2.02 (3H, s, Ad), 7.54 (1H,dd, 3J = 8.6 Hz, J = 0.8 Hz, arom.), 7.70 (1H, d, 3J = 8.6 Hz, arom.), 10.4 (1H, d, J = 0.8 Hz, CHO);13C{1H} NMR (100 MHz, CDCl3) 30.3 (Ad), 35.8 (Ad), 44.1 (Ad), 55.2 (Ad), 119.6 (C-Br), 134.7(C-Br), 135.9 (C-S), 136.0 (CH), 136.5 (CH), 143.3 (C-CHO), 192.3 (CHO). Found: m/z 452.9317 Calcdfor C17H1879Br81BrNaOS: (M+Na)+, 452.9317. Compound 2a likely include DMF molecule in the solid.

Reference： [1]Toyota, Kozo; Mutoh, Hirotaka; Kishi, Hiroki; Mikami, Shinichi; Tanaka, Hiroki; Yoshida, Shuhei; Naganuma, Daisuke [Heterocycles, 2019, vol. 98, # 10, p. 1355 - 1374]

51
[ 34301-54-7 ]
(2R,3S)-3-(benzyloxy)-2-methyl-2,3-dihydro-4H-pyran-4-one [ No CAS ]
4-O-benzyl-2,6-dideoxy-1-adamantanethiol-β-D-hexopyranosid-3-ulose [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
71%	Stage #1: 1-Adamantanethiol With caesium carbonate; triethylamine In tetrahydrofuran at -10℃; for 0.0833333h; Inert atmosphere; Stage #2: (2R,3S)-3-(benzyloxy)-2-methyl-2,3-dihydro-4H-pyran-4-one In tetrahydrofuran at -10 - 0℃; for 4h; Inert atmosphere;

Reference： [1]Yalamanchili, Subbarao; Miller, William; Chen, Xizhao; Bennett, Clay S. [Organic Letters, 2019, vol. 21, # 23, p. 9646 - 9651]

52
[ 34301-54-7 ]
[ 40400-13-3 ]
(adamantan-1-yl)(2-iodobenzyl)sulfane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	Stage #1: 1-Adamantanethiol With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 0.5h; Schlenk technique; Stage #2: 2-Iodobenzyl bromide In N,N-dimethyl-d<SUB>6</SUB>-formamide at 20℃; Schlenk technique;

Reference： [1]Shan, Xiang-Huan; Wang, Mei-Mei; Tie, Lin; Qu, Jian-Ping; Kang, Yan-Biao [Organic Letters, 2020, vol. 22, # 2, p. 357 - 360]

53
[ 34301-54-7 ]
gold(III) tetrachloride trihydrate [ No CAS ]
2-(5-aminobenzo[h]quinolone)-3-(3-methyl-2-butenyl)-1,4-naphthoquinone [ No CAS ]
C₃₈H₃₆AuClN₂O₂S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83.42%	With sodium methylate In water at 110℃; for 0.5h; Microwave irradiation;	Synthesis of the complex (NQ-N^C)AuIII(SAd)Cl, 1 The ligand NQ-N^C (42 mg, 0.1 mmol), 1-adamantanethiol (HSAd) (16.8 mg, 0.1 mmol), HAuCl4.3H2O (39.4 mg, 0.1 mmol), and sodium methoxide (NaOMe) (27 mg, 0.5 mmol) were combined in 20 mL of water. This mixture was heated in a sealed vessel in a microwave reactor (maximum pressure: 3 bar; maximum power: 250 W). The reaction mixture was heated at 110°C for 30 min. After cooling, the product was filtered off, washed with water (5 mL) and diehylether (20 mL), and dried under vacuum (pale yellow solid (68 mg, 83.42% yield, and 0.1 mmol)). Anal. Calc. (%) for C38H36AuClN2O2S (816.1852): C, 55.85; H, 4.44; N, 3.43; Found (%): C,55.82; H, 4.43; N, 3.40. TOF-MS: 781.2163 [M -Cl]+. 1H NMR (CDCl3): d 9.84 (d, 1H, H-1,3J = 8.0 Hz), 8.88 (d, 1H, H-3, 3 J = 8.0 Hz),8.16-8.18 (m, 2H, H-c,f), 8.00-8.03 (m, 2H, H-d,e), 7.77-7.87 (m, 2H, H-Ar), 7.68-7.75 (m, 2H, H-Ar),7.39 (s, 1H, H-4), 5.19-5.24 (m, 1H, H-b), 4.74 (bs,1H, H-NH), 3.10 (d, 2H, H-a, 3J = 7.6 Hz), 1.94 (bs,3H, H-11), 1.86 (s, 3H, H-CH3), 1.64 (d, 6H, H-10,3J = 8.0 Hz), 1.50 (s, 3H, H-CH3), 1.25-1.34 (m, 6H,H-12). 13C NMR (CDCl3): d 187.6 (C=O), 182.3(C=O), 166.3 (C-8), 156.2, 147.5, 140.0, 136.3, 135.0,134.1, 132.7, 131.6, 128.6, 126.4, 125.0, 123.9, 119.4,112.3, 51.4 (C-9), 49.2 (C-10), 35.4 (C-12), 31.9 (C-11), 28.2, 23.4, 17.3.

Reference： [1]Abyar, Fatemeh; Tabrizi, Leila [BioMetals, 2020]

54
[ 34301-54-7 ]
[ 415725-18-7 ]
methyl 2-(2-(((3s,5s,7s)-adamantan-1-yl)thio)-1H-indol-3-yl)acetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With tris(2,2-bipyridine)ruthenium(II) hexafluorophosphate; <i>p</i>-toluidine In dimethyl sulfoxide at 20℃; for 3h; Irradiation; Inert atmosphere; Flow reactor;

Reference： [1]Betim, Hugo L. I.; Campos Delgado, Jose Antonio; Corrêa, Arlene G.; Kisukuri, Camila M.; Paixão, Márcio W.; Santos, Marilia S. [Organic Letters, 2020, vol. 22, # 11, p. 4266 - 4271]

55
[ 110-91-8 ]
[ 34301-54-7 ]
4-(((3s,5s,7s)-adamantan-1-yl)thio)morpholine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53%	With potassium permanganate; iodine; oxygen In N,N-dimethyl-formamide at 80℃; for 12h; Schlenk technique;

Reference： [1]Liu, Shengping; Qi, Zaojuan; Qian, Bo; Zhang, Zhang [Organic Letters, 2019]

56
[ 34301-54-7 ]
[ 4832-52-4 ]
C₂₃H₂₆S₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With trifluoroacetic acid; at 20℃;Sealed tube;	General procedure: In a typical experiment, trithioorthoester (initial concentration: 50 mM, 37.5 μmol, 1 equiv), thiol/selenol(initial concentration: 150 mM, 112.5 μmol, 3 equiv and TFA (initial concentration: 500 mM, 375 μmol, 10 equivor 50 mM, 37.5 μmol, 1 equiv) or FeCl3 (initial concentration: 50 mM, 37.5 μmol, 1 equiv or 5.0 mM, 3.75 μmol,0.1 equiv) were mixed in a dry, deoxygenated, deuterated solvent from stock solutions (total volume: 750 μL).The reactions were either performed in oven-dried, capped NMR tubes or scintillation vials (2 mL). Once all thereagents were added, the NMR tubes and vials were turned upside down three times in order to ensure propermixing. The progress of the reaction was monitored with 1H NMR spectroscopy after 1 h and 24 h of theaddition of acid.

Reference： [1]Synlett,2019,vol. 30,p. 1988 - 1994

57
[ 34301-54-7 ]
[ 401-67-2 ]
C₁₂H₁₆F₂OS [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
100%	With pyridine In dichloromethane at 20℃; for 2h;

Reference： [1]Brigham, Conor E.; Malapit, Christian A.; Lalloo, Naish; Sanford, Melanie S. [ACS Catalysis, 2020, vol. 10, # 15, p. 8315 - 8320]

58
[ 34301-54-7 ]
[ 131242-36-9 ]
C₁₄H₁₈N₂S₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	Stage #1: 1-Adamantanethiol With C₂₀H₁₈N₂O₄S₄ In dichloromethane at 0℃; for 0.0833333h; Stage #2: 2-sulfanylpyrimidine With lithium carbonate In dichloromethane at 0 - 20℃; for 1h;
70%	Stage #1: 1-Adamantanethiol With 5,10-dihydro-6,9-dioxa-7,8-dithia-benzocyclooctene In methanol at -78℃; for 0.5h; Stage #2: 2-sulfanylpyrimidine With tris(pentafluorophenyl)borate In dichloromethane for 4h;	64 Synthesis of compound 4a: At -78, add adamantane mercaptan (16.8mg, 0.1mmol) in methanol (1mL) solution dropwise to the methanol (1mL) solution of 6 (24.0mg, 0.12mmol, 1.2equiv), and react for 0.5 hours to remove the methanol ,Add 2-mercaptopyrimidine (12.3mg, 0.11mmol, 1.1equiv), B(C6F5)3 (0.5mg, 0.001mmol, 1mol%) and dichloromethane (1mL), react for four hours, remove the solvent, and obtain the result by column chromatography White solid 4a (23.9 mg, 70%).

Reference： [1]Xue, Jiahui; Jiang, Xuefeng [Organic Letters, 2020, vol. 22, # 20, p. 8044 - 8048]
[2]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN113527022, 2021, A Location in patent: Paragraph 0381-0384

59
[ 34301-54-7 ]
[ 106-47-8 ]
C₁₆H₂₀ClNS₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	Stage #1: 4-chloro-aniline With 5,10-dihydro-6,9-dioxa-7,8-dithia-dibenzo[<i>a</i>,<i>c</i>]cyclodecene; tris(pentafluorophenyl)borate In 1,4-dioxane at 20℃; for 4h; Stage #2: 1-Adamantanethiol With lithium carbonate In 1,4-dioxane at 20℃; for 8h;	42 Synthesis of compound 3s: Add 4-chloroaniline (12.7 mg, 0.1 mmol, 1.0 equiv), 5 (29.0 mg, 0.105 mmol, 1.05 equiv), B(C6F5) 3 (0.5 mg, 0.001 mmol, 1 mol%) to the reaction tube and redistill 1,4-dioxane (0.25mL), stirred at room temperature for 4 hours, and then added 1-adamantanethiol (20.1mg, 0.12mmol, 1.2equiv) and lithium carbonate (7.4mg, 0.1mmol, 1.0equiv) After stirring for 8 hours at room temperature, the solvent was removed, and column chromatography gave a white solid 3s (33.3 mg, 93%).
85%	Stage #1: 1-Adamantanethiol With C₂₀H₁₈N₂O₄S₄ In dichloromethane at 0℃; for 0.0833333h; Stage #2: 4-chloro-aniline With dmap In dichloromethane at 0 - 20℃; for 1h;

Reference： [1]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN113527022, 2021, A Location in patent: Paragraph 0293-0296
[2]Xue, Jiahui; Jiang, Xuefeng [Organic Letters, 2020, vol. 22, # 20, p. 8044 - 8048]

60
chloroauric acid [ No CAS ]
[ 34301-54-7 ]
[ 14866-33-2 ]
[ 2071-20-7 ]
copper dichloride [ No CAS ]
[Au₄Cu₄(bis(diphenylphosphino)methane)₂(Sadm)₅]Br [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: chloroauric acid; tetraoctyl ammonium bromide In dichloromethane at 20℃; for 0.25h; Stage #2: 1-Adamantanethiol; bis-diphenylphosphinomethane; copper dichloride In dichloromethane for 0.5h; Stage #3: With sodium tetrahydroborate In dichloromethane; water at 20℃; for 12h;

Reference： [1]Fang, Yaping; Bao, Kang; Zhang, Peng; Sheng, Hongting; Yun, Yapei; Hu, Shu-Xian; Astruc, Didier; Zhu, Manzhou [Journal of the American Chemical Society, 2021, vol. 143, # 4, p. 1768 - 1772]

61
[ 34301-54-7 ]
[ 139152-08-2 ]
[ 1417158-52-1 ]

Yield	Reaction Conditions	Operation in experiment
99%	With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 20h;	Preparation of compound 3 1 (0.591 g, 3.00 mmol) and 2 (1.262 g, 7.50 mmol) were dissolved in DMF (18 mL), next K2CO3 (4.14 g, 30 mmol) was added in two portions and the reaction mixture was stirred for 20 h at room temperature. After that time the reaction mixture was poured into ice-water. The resulting solid was filtered, washed with water, dried, taken into reflux in CH3OH (20 mL) for 30 min in order to remove soluble impurities. Pale yellow amorphous solid (1.370 g, 99%) was obtained. M.p. 219-221 °C. Rf = 0.46 (n-hexane:EtOAc 7:1). Anal. Calc. for C28H32N2S2: C, 73.00; H, 7.00; N, 6.08; S, 13.92. Found: C, 72.88; H, 7.00; N, 6.06; S, 14.01.1H NMR (400 MHz, DMSO-d6) δ = 8.15 (s, 2H), 2.02 (bs, 6H), 1.89 (bs, 12H), 1.63 (bs, 12H). 13C NMR (101 MHz, DMSO-d6) δ = 144.8, 139.0, 115.4, 112.8, 52.1, 42.90, 35.3, 29.5. MS (ES) 483 [M+Na]+, 499 [M+K]+.

Reference： [1]Kryjewski, Michal; Nowak, Michal; Kasprzycki, Piotr; Fita, Piotr; Radzewicz, Czeslaw; Goslinski, Tomasz; Mielcarek, Jadwiga [Inorganic Chemistry Communications, 2013, vol. 27, p. 56 - 59]

62
[ 34301-54-7 ]
[ 37112-31-5 ]
2-adamantan-1-ylthio-6,8-dioxabicyclo[3.2.1]octan-4-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With triethylamine In dichloromethane at 20℃; for 24h;	2-Adamantan-1-yl-thio-6,8-dioxabicyclo[3.2.1]octan-4-one (9) To a solution of levoglucosenone 1 (0.73g, 0.2 mmol) in dichloromethane (10 mL) a solution of 1-thio-adamantane 8 (0.84g, 0.2 mmol) in 5 mL of dichloromethane and 0.5.mL of triethylamine was added dropwise. The reaction mixture was stirred at room temperature for 24 h. After evaporation of the solvent, the syrupy residue was purified by, crystallization from methanol. Yield (1.08g, 74%), colorless crystals, m.p.120-121°C, Rf = 0.39 (1:4, hexane-EtOAc); []D -128.2 (c 0.84, CHCl3); 1H NMR (400 MHz, CDCl3) δ: 3.96- 4.07 (m, 2H, H-6endo and H-6exo), 3.58 (m, 1H, H-4), 3.09( dd, 1H, J3eq,4 8.1 Hz, Jgem 17.8 Hz, H-3eq), 2.05 (dd, 1H, J3ax,4 1.5Hz, H-3ax), 2.09(s, 3H), 1.96 (s, 6H), 1.69 (s,9H). 13C NMR (100 MHz, CDCl3): 30.7, 32.2 (C-4, C-S), 43.1, 38.7 (C-3), 47.8, 72.4 (C-6), 91.9 (C-5), 127.2 (C-1), 202.0 (C-2, C=O).

Reference： [1]Witczak, Zbigniew J.; Mauger, Anastasia; Bielski, Roman; Mencer, Donald E. [Arkivoc, 2021, vol. 2021, # 4, p. 268 - 279]

63
[ 959150-64-2 ]
[ 34301-54-7 ]
4-(adamantylthio)-2-(2,6-dioxopiperidin-3-yl)isoindoline-1,3-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With [Pd2(dba)3]*CHCl3; N-ethyl-N,N-diisopropylamine; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; In 1,4-dioxane; at 90.0℃;Schlenk technique; Inert atmosphere;	General procedure: To a flame-dried Schlenk flask was added the following insequence under an inert atmosphere of argon: 4-iodothalidomide4a (200 mg, 0.52 mmol), Pd2(dba)3CHCl3 (16 mg, 0.016 mmol)and XantPhos (16 mg, 0.032 mmol), 1,4-dioxane (2 mL), diisopropylethylamine(0.50 mL, 1.04 mmol) and the required thiol(0.57 mmol). The reaction mixturewas heated to 90 C with stirringfor 16 h, cooled to room temperature and diluted with ethyl acetate(10 mL). The mixture was filtered through a pad of Celite, washingwith ethyl acetate and DCM (ca. 20 mL each). The filtrate wasadsorbed to silica and purified via flash column chromatography onsilica to furnish the desired sulfide-functionalised thalidomidederivative.

Reference： [1]European Journal of Medicinal Chemistry,2021,vol. 217

64
[ 34301-54-7 ]
2'-maleimidomethyl-3,4-ethylenedioxythiophene [ No CAS ]
C₂₁H₂₅NO₄S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine In dichloromethane at 20℃; for 8h; Inert atmosphere;	7.7A Example 7A: Synthesis of EDOT-MA adamantane Into a round bottom flask equipped with a magnetic stirring bar were added EDOT-MA (0.20 g, 0.80 mmol), 1-adamantanethiol (0.135 g, 0.80 mmol), triethylamine (111 mI_, 0.80 mmol), and dry dichloromethane (5 ml_). The reaction mixture was stirred at room temperature under nitrogen atmosphere for 8 h. The dichloromethane (20 mL) was added to the reaction mixture and the solution was washed with water (3 x 20 mL). The solution was dried over anhydrous sodium sulfate, filtered and dichloromethane was removed by evaporation under reduced pressure. The crude product was purified by column chromatography using pet ether: ethyl acetate (80:20, v/v) as an eluent to afford pure EDOT-MA_adamantane. XH NMR (400 MHz, CDCh): d=6.34 (d, 2H), 4.41 (t, 1H), 4.21-4.17 (m, 1H), 3.99-3.87 (m, 3H), 3.73-3.67 (m, 1H), 3.30-3.22 (m, 1H), 2.75-2.67 (m, 1H), 2.11 (s, 3H), 1.95 (s, 6H), 1.72 (s, 6H); 13C NMR (100 MHz, CDCh): d= 176.9, 174.6, 141.0, 140.6, 100.3, 99.9, 70.4, 66.3, 47.3, 43.7, 43.0, 39.2, 39.1, 36.0, 30.0, 29.7 ppm.

Reference： [1]Current Patent Assignee: MARTIN DAVID C; NAGANE SAMADHAN SURESH - WO2021/41874, 2021, A1 Location in patent: Page/Page column 29; 30

65
[ 34301-54-7 ]
sodium adamantane-1-thiolate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
100%	With sodium In ethanol at 20℃; for 3h; Inert atmosphere;	General procedure for the synthesis of sodium aryl or alkyl thiolates General procedure: Sodium aryl or alkyl thiolates were prepared according to a procedure described in the literature.2Under N2 atmosphere, sodium (10 mmol, 1.0 eq., 240 mg) was dissolved in 30 mL of absoluteethanol at room temperature. Careful: strong gas evolution (H2) To the generated solution wasadded 2-mercaptopyridine (10 mmol, 1.0 eq, 1.11 g) portion wise with stirring. The reaction wasstirred at the rt for 3h. The solvent was removed on the rotary evaporator. The resulting yellowishsolid was suspended in 50 ml of diethyl ether and sonicated for 3 hours. The solid was washed withEt2O (100 mL) and collected by filtration and dried under high vacuum to afford the correspondingsodium thiolate salt in quantitative yield.

Reference： [1]König, Burkhard; Wang, Hua; Wang, Shun [Chem, 2021, vol. 7, # 6, p. 1653 - 1665]

66
[ 34301-54-7 ]
2-[(4-methoxyphenyl)sulfanyl]pyridine [ No CAS ]
1-adamantyl (4-methoxy)phenyl sulfide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With bis(acetylacetonate)nickel(II); manganese; lithium hexamethyldisilazane; 1,2-bis-(dicyclohexylphosphino)ethane In toluene at 160℃; for 24h; Inert atmosphere;	General procedure for the synthesis of alkyl aryl sulfifides General procedure: Thiols (1 mmol), aryl 2-pyridyl thioethers (0.5 mmol), Ni(acac)2 (13 mg, 0.05 mmol), dcype (42 mg, 0.1 mmol), Mn (55 mg, 1 mmol), and LiHMDS (1.0 M in toluene,1.5 mL, 1.5 mmol) were successively added into a 15 mL sealed tube. The mixture was stirred in a 160 C oil bath under nitrogen for 24 h. Upon completion of the reaction as indicated by TLC, the mixture was diluted with EtOAc and then filtered through a pad of Celite. The solvent was removed under vacuum. The residue was purified on a silica gel column (petroleum ether/ethyl acetate) to give the pure target product.

Reference： [1]Wang, Cheng-Yi; Tian, Rui; Zhu, Yong-Ming [Tetrahedron, 2021, vol. 99]

67
[ 34301-54-7 ]
[ 723-46-6 ]
C₂₀H₂₅N₃O₃S₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	Stage #1: sulfamethoxazole With 5,10-dihydro-6,9-dioxa-7,8-dithia-dibenzo[<i>a</i>,<i>c</i>]cyclodecene; tris(pentafluorophenyl)borate In 1,4-dioxane at 20℃; for 24h; Stage #2: 1-Adamantanethiol With lithium carbonate In 1,4-dioxane at 20℃; for 8h;	60 Synthesis of compound 3al: Add sulfisoxazole (25.3mg, 0.1mmol, 1.0equiv), 3al (29.0mg, 0.105mmol, 1.05equiv), B(C6F5)3 (2.5mg, 0.001mmol, 5mol%) to the reaction tube and redistill 1,4-dioxane (0.25mL), stirred at room temperature for 24 hours, and then added 1-adamantyl mercaptan (20.1mg, 0.12mmol, 1.2equiv) and lithium carbonate (7.4mg, 0.1mmol, 1.0equiv ), stirring at room temperature for 8 hours, removing the solvent, and column chromatography to obtain 3al (31.4 mg, 65%) as a white solid.

Reference： [1]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN113527022, 2021, A Location in patent: Paragraph 0365-0368

68
[ 34301-54-7 ]
[ 90-41-5 ]
C₂₂H₂₅NS₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	Stage #1: 2-phenylaniline With 5,10-dihydro-6,9-dioxa-7,8-dithia-dibenzo[<i>a</i>,<i>c</i>]cyclodecene; tris(pentafluorophenyl)borate In 1,4-dioxane at 20℃; for 12h; Stage #2: 1-Adamantanethiol With lithium carbonate In 1,4-dioxane at 20℃; for 8h;	46 Synthesis of compound 3w: Add 2-phenylaniline (11.8 mg, 0.1 mmol, 1.0 equiv), 5 (29.0 mg, 0.105 mmol, 1.05 equiv), B(C6F5) 3 (0.5 mg, 0.001 mmol, 1 mol%) and weight to the reaction tube Steamed 1,4-dioxane (0.25mL), stirred at room temperature for 12 hours, and then added 1-adamantanethiol (20.1mg, 0.12mmol, 1.2equiv) and lithium carbonate (7.4mg, 0.1mmol, 1.0equiv ), stirring at room temperature for 8 hours, removing the solvent, and column chromatography to obtain a white solid 3w (28.5 mg, 86%).

Reference： [1]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN113527022, 2021, A Location in patent: Paragraph 0309-0312

69
[ 372-19-0 ]
[ 34301-54-7 ]
C₁₆H₂₀FNS₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	Stage #1: meta-fluoroaniline With 5,10-dihydro-6,9-dioxa-7,8-dithia-dibenzo[<i>a</i>,<i>c</i>]cyclodecene; tris(pentafluorophenyl)borate In 1,4-dioxane at 20℃; for 12h; Stage #2: 1-Adamantanethiol With lithium carbonate In 1,4-dioxane at 20℃; for 8h;	47 Synthesis of compound 3x: Add 3-fluoroaniline (11.1 mg, 0.1 mmol, 1.0 equiv), 5 (29.0 mg, 0.105 mmol, 1.05 equiv), B(C6F5) 3 (0.5 mg, 0.001 mmol, 1 mol%) to the reaction tube and re-evaporate 1,4-dioxane (0.25mL), stirred at room temperature for 12 hours, and then added 1-adamantanethiol (20.1mg, 0.12mmol, 1.2equiv) and lithium carbonate (7.4mg, 0.1mmol, 1.0equiv) After stirring for 8 hours at room temperature, the solvent was removed, and column chromatography gave a bright yellow liquid 3x (26.2 mg, 77%).

Reference： [1]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN113527022, 2021, A Location in patent: Paragraph 0313-0316

70
[ 34301-54-7 ]
[ 372-39-4 ]
C₁₆H₁₉F₂NS₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	Stage #1: 3,5-difluoroaniline With 5,10-dihydro-6,9-dioxa-7,8-dithia-dibenzo[<i>a</i>,<i>c</i>]cyclodecene; tris(pentafluorophenyl)borate In 1,4-dioxane at 20℃; for 12h; Stage #2: 1-Adamantanethiol With lithium carbonate In 1,4-dioxane at 20℃; for 8h;	48 Synthesis of compound 3y: Add 3,5-difluoroaniline (12.9mg, 0.1mmol, 1.0equiv), 5 (29.0mg, 0.105mmol, 1.05equiv), B(C6F5)3 (0.5mg, 0.001mmol, 1mol%) to the reaction tube And redistilled 1,4-dioxane (0.25mL), stirred at room temperature for 12 hours, and then added 1-adamantanethiol (20.1mg, 0.12mmol, 1.2equiv) and lithium carbonate (7.4mg, 0.1mmol, 1.0 equiv), stirring at room temperature for 8 hours, removing the solvent, and column chromatography to obtain a bright yellow liquid 3y (25.1 mg, 70%).

Reference： [1]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN113527022, 2021, A Location in patent: Paragraph 0317-0320

71
[ 34301-54-7 ]
methyl (tert-butoxycarbonyl)-L-isoleucine-D-lysine [ No CAS ]
C₂₈H₄₉N₃O₅S₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
40%	Stage #1: methyl (tert-butoxycarbonyl)-L-isoleucine-D-lysine With 5,10-dihydro-6,9-dioxa-7,8-dithia-dibenzo[<i>a</i>,<i>c</i>]cyclodecene; tris(pentafluorophenyl)borate In 1,4-dioxane at 20℃; for 4h; Stage #2: 1-Adamantanethiol With lithium carbonate In 1,4-dioxane at 20℃; for 8h;	57 Synthesis of compound 3ah: Add methyl (tert-butoxycarbonyl)-L-isoleucine-D-lysine (37.3 mg, 0.1 mmol, 1.0 equiv), 5 (29.0 mg, 0.105 mmol, 1.05 equiv), B to the reaction tube (C6F5)3 (1.0mg, 0.002mmol, 2mol%) and redistilled 1,4-dioxane (0.25mL), stirred at room temperature for 4 hours, and then added dodecanethiol (24.2mg, 0.12mmol, 1.2 equiv) and lithium carbonate (7.4 mg, 0.1 mmol, 1.0 equiv), stirred at room temperature for 8 hours, removed the solvent, and column chromatography gave a white solid 3ah (24.2 mg, 40%).

Reference： [1]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN113527022, 2021, A Location in patent: Paragraph 0353-0356

72
[ 34301-54-7 ]
[ 769-92-6 ]
C₂₀H₂₉NS₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	Stage #1: 4-tert-Butylaniline With 5,10-dihydro-6,9-dioxa-7,8-dithia-dibenzo[<i>a</i>,<i>c</i>]cyclodecene; tris(pentafluorophenyl)borate In 1,4-dioxane at 20℃; for 4h; Stage #2: 1-Adamantanethiol With lithium carbonate In 1,4-dioxane at 20℃; for 8h;	44 Synthesis of compound 3u: Add 4-tert-butylaniline (14.9mg, 0.1mmol, 1.0equiv), 5 (29.0mg, 0.105mmol, 1.05equiv), B(C6F5)3 (0.5mg, 0.001mmol, 1mol%) and Redistilled 1,4-dioxane (0.25mL), stirred at room temperature for 4 hours, and then added 1-adamantanethiol (20.1mg, 0.12mmol, 1.2equiv) and lithium carbonate (7.4mg, 0.1mmol, 1.0 equiv), stirring at room temperature for 8 hours, removing the solvent, and column chromatography to obtain a white solid 3u (28.5mg, 75%).

Reference： [1]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN113527022, 2021, A Location in patent: Paragraph 0301-0304

73
[ 34301-54-7 ]
[ 35250-53-4 ]
C₁₆H₂₂N₂S₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
50%	Stage #1: 1-Adamantanethiol With 5,10-dihydro-6,9-dioxa-7,8-dithia-benzocyclooctene In methanol at -78℃; for 0.5h; Stage #2: 2-(2-mercaptoethyl)pirazine With tris(pentafluorophenyl)borate In dichloromethane for 4h;	65 Synthesis of compound 4b: At -78, add adamantane mercaptan (16.8mg, 0.1mmol) in methanol (1mL) solution dropwise to the methanol (1mL) solution of 6 (24.0mg, 0.12mmol, 1.2equiv), and react for 0.5 hours to remove the methanol , Add 2-pyrazinylethanethiol (15.4mg, 0.11mmol, 1.1equiv), B(C6F5)3 (0.5mg, 0.001mmol, 1mol%) and dichloromethane (1mL), react for four hours, remove the solvent Column chromatography to obtain a colorless liquid 4b (18.5mg, 50%).

Reference： [1]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN113527022, 2021, A Location in patent: Paragraph 0385-0388

74
[ 34301-54-7 ]
[ 7652-46-2 ]
C₁₆H₂₅NO₃S₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
52%	Stage #1: 1-Adamantanethiol With 5,10-dihydro-6,9-dioxa-7,8-dithia-benzocyclooctene In methanol at -78℃; for 0.5h; Stage #2: Ac-Cys-OMe With tris(pentafluorophenyl)borate In dichloromethane for 4h;	68 Synthesis of compound 4e: At -78, add adamantane mercaptan (16.8mg, 0.1mmol) in methanol (1mL) solution dropwise to the methanol (1mL) solution of 6 (24.0mg, 0.12mmol, 1.2equiv), and react for 0.5 hours to remove the methanol , Add acetylcysteine methyl ester (19.5mg, 0.11mmol, 1.1equiv), B(C6F5)3 (1.0mg, 0.001mmol, 2mol%) and dichloromethane (1mL), react for four hours, remove the solvent, Column chromatography gave 4e (21.2 mg, 52%) as a white solid.

Reference： [1]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN113527022, 2021, A Location in patent: Paragraph 0397-0400

75
[ 34301-54-7 ]
C₂₃H₂₅N₃O₆S₃ [ No CAS ]
C₃₃H₃₉N₃O₆S₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
40%	Stage #1: 1-Adamantanethiol With 5,10-dihydro-6,9-dioxa-7,8-dithia-benzocyclooctene In methanol at -78℃; for 0.5h; Stage #2: C₂₃H₂₅N₃O₆S₃ With tris(pentafluorophenyl)borate In dichloromethane for 4h;	69 Synthesis of compound 4f: At -78, add adamantane mercaptan (16.8mg, 0.1mmol) in methanol (1mL) solution dropwise to the methanol (1mL) solution of 6 (24.0mg, 0.12mmol, 1.2equiv), and react for 0.5 hours to remove the methanol , Add tripeptide (51.8mg, 0.11mmol, 1.1equiv), B(C6F5)3 (1.0mg, 0.001mmol, 2mol%) and dichloromethane (1mL), react for four hours, remove the solvent, column chromatography to obtain white Solid 4f (28.2 mg, 40%).

Reference： [1]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN113527022, 2021, A Location in patent: Paragraph 0401-0404

76
[ 19879-84-6 ]
[ 34301-54-7 ]
C₂₄H₃₄O₉S₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
57%	Stage #1: 1-Adamantanethiol With 5,10-dihydro-6,9-dioxa-7,8-dithia-benzocyclooctene In methanol at -78℃; for 0.5h; Stage #2: tetraacetyl thioglucose With tris(pentafluorophenyl)borate In dichloromethane for 4h;	70 Synthesis of compound 4g: At -78, add adamantane mercaptan (16.8mg, 0.1mmol) in methanol (1mL) solution dropwise to the methanol (1mL) solution of 6 (24.0mg, 0.12mmol, 1.2equiv), and react for 0.5 hours to remove the methanol , Add glucosinolate (40.0mg, 0.11mmol, 1.1equiv), B(C6F5)3 (1.0mg, 0.001mmol, 2mol%) and dichloromethane (1mL), react for four hours, remove the solvent, and column chromatography gives white Solid 4g (33.8mg, 57%).

Reference： [1]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN113527022, 2021, A Location in patent: Paragraph 0405-0408

77
[ 34301-54-7 ]
[ 57-68-1 ]
C₂₂H₂₈N₄O₂S₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	Stage #1: sulfadimesine With 5,10-dihydro-6,9-dioxa-7,8-dithia-dibenzo[<i>a</i>,<i>c</i>]cyclodecene; tris(pentafluorophenyl)borate In 1,4-dioxane at 20℃; for 24h; Stage #2: 1-Adamantanethiol With lithium carbonate In 1,4-dioxane at 20℃; for 8h;	55 Synthesis of compound 3af:: Add sulfamethazine (27.8 mg, 0.1 mmol, 1.0 equiv), 5 (29.0 mg, 0.105 mmol, 1.05 equiv), B (C6F5) 3 (2.5 mg, 0.005 mmol, 5 mol%) to the reaction tube and redistill 1,4-dioxane (0.25mL), stirred at room temperature for 24 hours, and then added 1-adamantanethiol (20.1mg, 0.12mmol, 1.2equiv) and lithium carbonate (7.4mg, 0.1mmol, 1.0equiv) After stirring for 8 hours at room temperature, the solvent was removed, and column chromatography gave 3af (37.6 mg, 74%) as a white solid.

Reference： [1]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN113527022, 2021, A Location in patent: Paragraph 0345-0348

78
[ 34301-54-7 ]
[ 149104-90-5 ]
C₁₈H₂₂OS₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
52%	Stage #1: 4-acetylphenylboronic acid With 5,10-dihydro-6,9-dioxa-7,8-dithia-dibenzo[<i>a</i>,<i>c</i>]cyclodecene; [2,2]bipyridinyl; tetrakis(actonitrile)copper(I) hexafluorophosphate In dichloromethane Inert atmosphere; Stage #2: 1-Adamantanethiol In dichloromethane for 6h; Inert atmosphere;	13 Synthesis of compound 1m: Add 4-acetophenone boronic acid (24.5mg, 0.15mmol, 1.5equiv), 5 (27.6mg, 0.10mmol, 1equiv), Cu(MeCN)4PF6 (3.7mg, 0.01mmol, 10mol%) to the reaction tube,2,2'-Bipyridine (3.1mg, 0.02mmol, 20mol%) and redistilled dichloromethane (1mL), replace nitrogen, react for 24 hours, filter, add adamantanethiol (20.2mg, 0.12mmol, 1.2 equiv), react for 6 hours, remove the solvent, and obtain 1m (18.2 mg, 52%) as a pale yellow solid by column chromatography.

Reference： [1]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN113527022, 2021, A Location in patent: Paragraph 0177-0180

79
[ 34301-54-7 ]
[ 873-74-5 ]
C₁₇H₂₀N₂S₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	Stage #1: 4-Aminobenzonitrile With 5,10-dihydro-6,9-dioxa-7,8-dithia-dibenzo[<i>a</i>,<i>c</i>]cyclodecene; tris(pentafluorophenyl)borate In 1,4-dioxane at 20℃; for 12h; Stage #2: 1-Adamantanethiol With lithium carbonate In 1,4-dioxane at 20℃; for 8h;	45 Synthesis of compound 3v: Add 4-cyanoaniline (11.8mg, 0.1mmol, 1.0equiv), 5 (29.0mg, 0.105mmol, 1.05equiv), B(C6F5)3 (0.5mg, 0.001mmol, 1mol%) and weight to the reaction tube. Steamed 1,4-dioxane (0.25mL), stirred at room temperature for 12 hours, and then added 1-adamantanethiol (20.1mg, 0.12mmol, 1.2equiv) and lithium carbonate (7.4mg, 0.1mmol, 1.0equiv ), stirring at room temperature for 8 hours, removing the solvent, and column chromatography to obtain a white solid 3v (28.5 mg, 86%).

Reference： [1]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN113527022, 2021, A Location in patent: Paragraph 0305-0308

80
[ 34301-54-7 ]
[ 106-40-1 ]
C₁₆H₂₀BrNS₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
98%	Stage #1: 4-bromo-aniline With 5,10-dihydro-6,9-dioxa-7,8-dithia-dibenzo[<i>a</i>,<i>c</i>]cyclodecene; tris(pentafluorophenyl)borate In 1,4-dioxane at 20℃; for 4h; Stage #2: 1-Adamantanethiol With lithium carbonate In 1,4-dioxane at 20℃; for 8h;	43 Synthesis of compound 3t: Add 4-bromoaniline (17.2 mg, 0.1 mmol, 1.0 equiv), 5 (29.0 mg, 0.105 mmol, 1.05 equiv), B(C6F5) 3 (0.5 mg, 0.001 mmol, 1 mol%) to the reaction tube and redistill 1,4-dioxane (0.25mL), stirred at room temperature for 4 hours, and then added 1-adamantanethiol (20.1mg, 0.12mmol, 1.2equiv) and lithium carbonate (7.4mg, 0.1mmol, 1.0equiv) After stirring at room temperature for 8 hours, the solvent was removed, and column chromatography gave a white solid 3t (39.4 mg, 98%).

Reference： [1]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN113527022, 2021, A Location in patent: Paragraph 0297-0300

81
[ 61-54-1 ]
[ 34301-54-7 ]
C₂₀H₂₆N₂S₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
52%	Stage #1: tryptamine With 5,10-dihydro-6,9-dioxa-7,8-dithia-dibenzo[<i>a</i>,<i>c</i>]cyclodecene; tris(pentafluorophenyl)borate In 1,4-dioxane at 20℃; for 4h; Stage #2: 1-Adamantanethiol With lithium carbonate In 1,4-dioxane at 20℃; for 8h;	58 Synthesis of compound 3aj: Add tryptamine (16.0 mg, 0.1 mmol, 1.0 equiv), 5 (29.0 mg, 0.105 mmol, 1.05 equiv) to the reaction tube,B(C6F5)3(0.5mg, 0.001mmol, 1mol%)And redistilled 1,4-dioxane (0.25mL),Stir at room temperature for 4 hours, then add adamantane mercaptan (20.1 mg, 0.12 mmol, 1.2 equiv) and lithium carbonate (7.4 mg, 0.1 mmol, 1.0 equiv), stir at room temperature for 8 hours, remove the solvent, and column chromatography to obtain a colorless liquid 3aj (20.3 mg, 52%).

Reference： [1]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN113527022, 2021, A Location in patent: Paragraph 0357-0360

82
[ 34301-54-7 ]
[ 65094-22-6 ]
(adamantan-1-yl)(difluoromethyl)sulfane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	Stage #1: 1-Adamantanethiol; diethyl (bromodifluoromethyl)phosphonate With potassium hydroxide In water; acetonitrile at 0℃; for 0.25h; Sealed tube; Stage #2: diethyl (bromodifluoromethyl)phosphonate In water; acetonitrile at 0 - 20℃; for 1.5h; Sealed tube; chemoselective reaction;	4.2. General procedure General procedure: The starting material (2 mmol) was added to a sealed tube holding 20 mL of a 1:1 mixture of acetonitrile/water and KOH (40 mmol), whichwas cooled using an ice bath. The mixture was vigorously mixed for 15min and then phosphonate 1 (4 mmol) was added to the mixture in oneportion, and mixing and cooling was maintained for an additional 15 -60 min, followed by ~30 min - 2.5 h at r.t. The reaction mixture wasthen diluted with ether (10 mL) and the organic phase separated. Thewater phase was further washed with ether (10 mL). The combinedorganic phase was dried over anhydrous Na2SO4 and the solvent evaporatedto provide a crude product which was purified using columnchromatography on silica gel

Reference： [1]Gershonov, Eytan; Amir, Dafna; Redy-Keisar, Orit; Binyamin, Iris; Yehezkel, Lea; Marciano, Daniele; Drug, Eyal; Fridkin, Gil; Zafrani, Yossi [Journal of Fluorine Chemistry, 2021, vol. 250]

83
[ 34301-54-7 ]
[ 51171-25-6 ]

Yield	Reaction Conditions	Operation in experiment
90%	With disulfur dichloride; triethylamine In diethyl ether at -78℃; Inert atmosphere;

Reference： [1]Gong, Kai; Jiang, Xuefeng; Zhou, Yilin [Green Chemistry, 2021, vol. 23, # 24, p. 9865 - 9869]

84
[ 34301-54-7 ]
[ 30979-75-0 ]

Yield	Reaction Conditions	Operation in experiment
92%	With cerium(III) bromide; dihydrogen peroxide In tetrahydrofuran; water at 20℃; for 0.1 - 1.5h;	6 Example 6 1f (1mmol, 168.3mg) was dissolved in THF (2ml), CeBr3 (0.02mmol, 7.6mg) and H2O2 aqueous solution (30wt%, 0.6mmol, 61.3μl) were successively added to the mixture, and the reaction was stirred at room temperature 0.1-1.5h. After completion of the reaction, the reaction was quenched with Na2S2O3 solution (0.1M, 1.5ml) and extracted with ethyl acetate (30ml). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (3 x 10 ml). The organic phases were combined, washed with water in sequence, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 2f (yield: 92%).

Reference： [1]Current Patent Assignee: BEIJING UNIVERSITY OF CHINESE MEDICINE - CN113860982, 2021, A Location in patent: Paragraph 0043-0045

85
[ 10276-21-8 ]
[ 34301-54-7 ]
2-(1-adamantylsulfanyl)-3,5,5-trimethylcyclohex-2-en-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95.9%	Stage #1: 1-Adamantanethiol With sodium ethanolate In ethanol at 20℃; for 0.166667h; Inert atmosphere; Stage #2: isophorone oxide In ethanol at 20℃; Inert atmosphere;	1.c Example 1c. Synthesis of 2-(1-adamantylsulfanyl)-3,5,5-trimethyl-cyclohex-2-en-1-one A solution of sodium ethoxide (21.0 %, 23.6 mL, 0.0632 mol) in ethanol (200 mL) was sparged with N2 then treated with adamantane- 1 -thiol (95.0 %, 44.8 g, 0.253 mol). The mixture was stirred at room temp under N2 for 10 min, then 4,4,6-trimethyl-7-oxabicyclo[4.1.0]heptan-2-one (39.0 g, 0.253 mol) was added. The flask was capped, and the mixture continued to stir at room temperature. After 10 min, reaction mixture was quenched with water, then the solid precipitate was isolated and dried by vacuum filtration to give 2-(1-adamantylsulfanyl)-3,5,5- trimethyl-cyclohex-2-en-1-one (73.9 g, 0.243 mol, yield: 95.9 %) as an off-white solid.
95.9%	Stage #1: 1-Adamantanethiol With sodium ethanolate In ethanol at 20℃; for 0.166667h; Inert atmosphere; Stage #2: isophorone oxide In ethanol at 20℃; for 0.166667h; Inert atmosphere; Sealed tube;	1.1.c Example 1c. Synthesis of 2-(1-adamantylsulfanyl)-3,5,5-trimethyl-cyclohex-2-en-1-one A solution of sodium ethoxide (21.0 %, 23.6 mL, 0.0632 mol) in ethanol (200 mL) was sparged with N2 then treated with adamantane- 1 -thiol (95.0 %, 44.8 g, 0.253 mol). The mixture was stirred at room temp under N2 for 10 min, then 4,4,6-trimethyl-7-oxabicyclo[4.1.0]heptan-2-one (39.0 g, 0.253 mol) was added. The flask was capped, and the mixture continued to stir at room temperature. After 10 min, reaction mixture was quenched with water, then the solid precipitate was isolated and dried by vacuum filtration to give 2-(1-adamantylsulfanyl)-3,5,5- trimethyl-cyclohex-2-en-1-one (73.9 g, 0.243 mol, yield: 95.9 %) as an off-white solid.

Reference： [1]Current Patent Assignee: LIGHTWAVE LOGIC - WO2021/263164, 2021, A1 Location in patent: Paragraph 0049; 0056-0057
[2]Current Patent Assignee: LIGHTWAVE LOGIC - WO2021/263164, 2021, A1 Location in patent: Paragraph 0049; 0056-0057

86
[ 512-56-1 ]
[ 34301-54-7 ]
[ 34895-33-5 ]

Yield	Reaction Conditions	Operation in experiment
80%	With calcium hydroxide In N,N-dimethyl-formamide at 80℃; for 2.6h; Sealed tube;	General Methylation Procedure A (DMF Conditions) General procedure: A 10-mL glass reaction tube fitted with a resealable Teflon valve wasequipped with a magnetic stir bar and charged with the heteroatomnucleophile substrate (1.0 mmol, 1.0 equiv), Ca(OH)2 (100 mg, 1.35mmol, 1.35 equiv), TMP (0.20 mL, 1.7 mmol, 1.7 equiv), and DMF (1.0mL). The flask was sealed and stirred at 80 °C (or at RT for some thiolsubstrates) until TLC indicated complete conversion. The reaction wasthen worked up as described below. Workup Procedure A After complete conversion, 1 N HCl (5 mL) was added and the mixturewas extracted with CH2Cl2 (10 mL). The organic phase was separated,washed with H2O (20 mL), dried over Na2SO4, filtered, and then concentratedin vacuo. The resulting residue was purified by silica gelcolumn chromatography to afford the desired methylated product.Workup Procedure B After complete conversion, petroleum ether (5 mL) was added, andthe solid was smashed into fine particles using a spatula and sonicatedfor 5 min. The resulting residue was then directly subjected to silicagel column chromatography to afford the desired methylated product.Workup Procedure C After complete conversion, CH2Cl2 (5 mL) was added, and the mixturewas filtered through a pad of Celite, washed with H2O (10 mL), andextracted with EtOAc (5 × 20 mL). The organic phase was separated,dried over Na2SO4, filtered, and concentrated in vacuo. The resultingresidue was purified by silica gel column chromatography to affordthe desired methylated product.

Reference： [1]Tang, Yu; Yu, Biao [Synthesis, 2022, vol. 54, # 10, p. 2373 - 2390]

87
[ 34301-54-7 ]
[ 604-69-3 ]
1-adamantyl 2,3,4,6-tetra-O-acetyl-1-deoxy-1-thio-α-D-glucopyranoside [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With boron trifluoride diethyl ether complex In dichloromethane at 0 - 20℃; for 19h; Inert atmosphere;

Reference： [1]Jensen, Henrik H.; Juul-Madsen, Line; Sandgaard, Tatjana L. P.; Trinderup, Helle H. [Journal of Organic Chemistry, 2022, vol. 87, # 6, p. 4154 - 4167]

88
[ 34301-54-7 ]
3,5-di-tert-butyl-6-(methoxymethyl)catechol [ No CAS ]
3-(adamantane-1-yl-thio)methyl-4,6-di-tert-butylcatechol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
58%	With glacial acetic acid at 60℃; for 6h; Inert atmosphere;	3.3. Synthesis of Catechol Thioethers 1-15 General procedure: The reaction of 3.5-di-tert-butyl-6-methoxymethylcatechol (0.54 g, 2 mmol) with thiols(2 mmol) was carried out in acetic acid (10 mL) under an inert atmosphere (argon) withstirring for 6 h at 60 C. After the reaction, 20 mL of water was added to the solution; theresulting precipitate was filtered off, dried in a vacuum, and recrystallized from acetonitrile.In case of catechol 6 the solution of concentrated hydrochloric acid (2 mL) was addedin water solution. The formed precipitate of pyridinium salt was filtered off, dried in avacuum. Compound 3 was previously prepared [25].

Reference： [1]Arsenyev, Maxim V.; Berberova, Nadezhda T.; Burmistrova, Daria A.; Fukin, Georgy K.; Poddel’sky, Andrey I.; Polovinkina, Maria A.; Pomortseva, Nadezhda P.; Smolyaninov, Ivan V. [Molecules, 2022, vol. 27, # 10]

Type	HazMat fee for 500 gram (Estimated)
Excepted Quantity	USD 0.00
Limited Quantity	USD 15-60
Inaccessible (Haz class 6.1), Domestic	USD 80+
Inaccessible (Haz class 6.1), International	USD 150+
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CAS No. :	34301-54-7	MDL No. :	MFCD00213530
Formula :	C₁₀H₁₆S	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	ADJJLNODXLXTIH-UHFFFAOYSA-N
M.W :	168.30	Pubchem ID :	99730
Synonyms :

Signal Word:	Danger	Class:	6.1
Precautionary Statements:	P301+P310-P305+P351+P338	UN#:	2811
Hazard Statements:	H301-H319	Packing Group:	Ⅲ
GHS Pictogram:

Precautionary Statements-General
Code	Phrase
P101	If medical advice is needed,have product container or label at hand.
P102	Keep out of reach of children.
P103	Read label before use
Prevention
Code	Phrase
P201	Obtain special instructions before use.
P202	Do not handle until all safety precautions have been read and understood.
P210	Keep away from heat/sparks/open flames/hot surfaces. - No smoking.
P211	Do not spray on an open flame or other ignition source.
P220	Keep/Store away from clothing/combustible materials.
P221	Take any precaution to avoid mixing with combustibles
P222	Do not allow contact with air.
P223	Keep away from any possible contact with water, because of violent reaction and possible flash fire.
P230	Keep wetted
P231	Handle under inert gas.
P232	Protect from moisture.
P233	Keep container tightly closed.
P234	Keep only in original container.
P235	Keep cool
P240	Ground/bond container and receiving equipment.
P241	Use explosion-proof electrical/ventilating/lighting/equipment.
P242	Use only non-sparking tools.
P243	Take precautionary measures against static discharge.
P244	Keep reduction valves free from grease and oil.
P250	Do not subject to grinding/shock/friction.
P251	Pressurized container: Do not pierce or burn, even after use.
P260	Do not breathe dust/fume/gas/mist/vapours/spray.
P261	Avoid breathing dust/fume/gas/mist/vapours/spray.
P262	Do not get in eyes, on skin, or on clothing.
P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
P272	Contaminated work clothing should not be allowed out of the workplace.
P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

[ CAS No. 34301-54-7 ] {[proInfo.proName]}

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[ 34301-54-7 ] Synthesis Path-Upstream 1~1

[ 34301-54-7 ] Synthesis Path-Downstream 1~88

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[ 34301-54-7 ]

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[ CAS No. 34301-54-7 ] {[proInfo.proName]}

Quality Control of [ 34301-54-7 ]

Related Doc. of [ 34301-54-7 ]

Product Details of [ 34301-54-7 ]

Safety of [ 34301-54-7 ]

Application In Synthesis of [ 34301-54-7 ]

[ 34301-54-7 ] Synthesis Path-Upstream 1~1

[ 34301-54-7 ] Synthesis Path-Downstream 1~88

Related Functional Groups of [ 34301-54-7 ]

Thiols

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Prevention

Response

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Disposal

Physical hazards

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Environmental hazards

Inquiry

Related Functional Groups of
[ 34301-54-7 ]